text:
The Clubhouse Breakfast Grill
Scot's porridge, heather honey, seeds
Avocado, sea salt tomatoes, toasted muffin
Yoghurt, berries
Fruit salad, vanilla syrup
Eggs any style, toast
Sweet cured or smoked bacon roll
add an egg £6
Tomatoes, seaweed salt, cracked pepper
Banana bread, yoghurt
Flowerpot muffins
Farmhouse toast, jam, honey
Smoked salmon 'Frittata', cheddar cheese
Findony ham, poached eggs, beans
The Clubhouse Breakfast Grill
Dry cured bacon, 'Wee' black pudding, haggis, grilled tomato, baked beans, 'Tattie' scone & your choice of egg,
fried, scrambled, poached
Breakfast Drinks
Virgin Mary
Freshly squeezed orange, grapefruit juice
Cafetiëre, The Gleneagles Blend coffee
Newby tea, Breakfast, Earl Grey, Assam, Darjeeling
Hot chocolate
Lunch Menu
Starters & Light Bites
Ham hock, lentil broth £8
"Scotch" egg, black cherry jam £11
Mushroom soup, crëme fraîche & Arran mustard £8
Classic Caesar £14
with boneless chicken £21 minted salmon £22
add salt & pepper jumbo prawn per piece 4£
Baked cauliflower, pear, blue cheese crumble £10
Smoked Scottish salmon, poached egg, asparagus £14
Prawn cocktail "Marie Rosé" £14
Beetroot, walnut salad, heather honeycomb £10
Sandwiches & Burgers
Clubhouse Club sandwich £17
Campbell's smoked salmon £11 King prawn "Marie Rosé" £11
Ham, chutney, smoked cheddar £10
Roast beef, horseradish, tomato £11
Shorthorn beef burger, chips, bacon & 'Rarebit' £17
Clubhouse Favourites
Mac 'n' cheese £12
Fish 'n' chips & tartare sauce £17
Steak & kidney 'n' oyster pudding £22
Fish pie £20
"Bangers 'n' mash", gravy £17
Shepherd's pie £22
Haggis neeps 'n' tatties
Vegetarian £11 Howie's lamb £11
Findony ham, poached egg, beans £16
"Steak 'n' mac" £21
Chick pea, spinach & harissa stew £19
From the Tandoor
Tandoor is a method of roasting meat and seafood over charcoal in a clay oven.
Lamb shoulder £25
Boneless chicken £22
Minted Scotch salmon £23
Monkfish "Tikka" £26
All served with naan bread, green apple, coriander & mint dressing
Stack onion rings Minted mushy peas Brown rice & curry
Pudding Pots & Cheese
Rice pudding, strawberry jam
Chocolate brownie
Butterscotch cheesecake
Raspberry trifle
Eton Mess
Selection of Scottish Cheese
3 cheese £10 5 cheese £16
Dinner Menu
"Scotch" egg, black cherry jam £11
Mushroom soup, crëme fraîche & Arran mustard £8
Prawn cocktail "Marie Rosé" £14
Beetroot, walnut salad, heather honeycomb £10
Rabbit, ham hock, leek terrine, piccalilli £13
Smoked Scottish salmon, poached egg, asparagus £14
Scallops, black pudding, curried cauliflower £15
Haggis neeps 'n' tatties
Vegetarian £11 Howie's lamb £11
Baked cauliflower, pear, blue cheese crumble £10
Main Courses
Crispy half roast duck, barley spelt & turnip top £26
Plaice, wilted chard, fennel, Thistly Cross ginger cider £25
Cheese pudding, kale pesto £19
Dornoch lamb rump slow cooked, fregola £25
Chick pea, spinach & harissa stew £19
Fish 'n' chips, tartare sauce £17
Shorthorn beef burger, chips, bacon & 'Rarebit' £17
Grass reared Perthshire, aged in a Himalayan salt wall chamber for 28 days
Sirloin min 9oz £28 Fillet min 7oz £30
Porterhouse steak on the bone min 14oz £40
add salt & black pepper jumbo prawn by the piece £4
From the Tandoor
Tandoor is a method of roasting meat and seafood over charcoal in a clay oven
Lamb shoulder £25
Boneless chicken £22
Minted Scotch salmon £23
Monkfish "Tikka" £26
All served with naan bread, green apple, coriander & mint dressing
Chips Brown rice & curry
Leaf buttered spinach add creamed mushrooms
Whipped horseradish mash 'n' gravy Summer salad, buttermilk dressing
Minted mushy peas
Puddings & Cheese
Scottish berry pudding
Burnt cream
Pear "Belle Hélëne"
Sticky toffee pudding, toffee sauce
Selection of Scottish Cheese
3 cheese £10 5 cheese £16
Younger Children's Menu
This menu is suitable for children under the age of 12 years who enjoy a simpler taste in food. Children who are willing and have the appetite to explore the culinary delights of The Clubhouse Bar and Grill are very welcome to dine from the main menu
Bon Appétit
Toddlers @ Gleneagles (Up to 3 years of age)
Carrot, cucumber sticks, hummus
Melon, strawberries, vanilla syrup
Cream vine tomato soup, croutons
Egg fried bread, crispy bacon
Boiled egg, plain or marmite soldiers
Buttered chopped egg in a cup
Main Courses
Macaroni cheese
Buttered chicken Korma style, fluffy rice
Mince and tatties
Scottish salmon, simply poached, mash, spinach
Stewart Tower ice cream, single ball, wafer
Bananas and custard
Individual fruit yoghurt
Poached pear, sugar syrup
Children @ Gleneagles (Up to 12 years old)
Melon, vanilla syrup, berries in season
Cream vine tomato soup, croutons
Classic Caesar salad
Salad Capresse, buffalo mozzarella. tomatoes, basil, rapeseed oil
Fried fish goujons, tomato ketchup
Bruschetta, creamed mushrooms
Prawn cocktail, Marie Rose sauce
Main Courses
Good old fish and chips in a basket, garden peas
Free range chicken fillet, grilled or breaded, french fries, tomato salsa
The "Gleneaglet" 4oz burger, tomatoes, bacon, cheese, french fries
"Steak Frit" Scotch minute steak, fries
Free range scrambled eggs on toast, add smoked salmon
Grilled catch of the day, new potatoes, steamed broccoli
Margherita pizza
Pasta of your choice, Bolognese style, simple olive oil and cheese or carbonara
Stewart Tower dairy ice cream coupe, chocolate flake
Banana split
Gleneagles apple pie, custard
Chocolate brownies, vanilla ice cream form Stewart Tower
Coupe fresh fruits in season, vanilla syrup
Auchterarder 70
Nuts - sea salt & rosemary 3.25
Pork Scratchings - apple sauce, mustard 2.75
Chips - béarnaise & peat smoked salt 2.95
Mac & Cheese – croquettes, ketchup 3.25
Onion Rings - Auchterarder 70 batter 3.25
Cheeseboard - pickle 9.95
Scotch Egg - fig jam 7.25
Chicken Pie - piccalilli 8.00
½ Pint Prawns - shell on 8.25
Fish Goujons - tartar sauce 6.95
Devilled Whitebait - aioli 5.95
Squid - nduja 5.25
Smoked Salmon - on rye 6.25
Chicken - BBQ sauce 5.95
Auchterarder 70 Sliders - relish 8.95
Ox Cheek - kimchi 6.95
Haggis - on toast 6.25
Sausage - bacon & egg 7.95
Rice Pudding - strawberry jam all 4.25
Chocolate Brownies
Butterscotch Cheesecake
Berry Mess
The Dormy Clubhouse
The Dormy Clubhouse Bar & Grill is a wonderful place to sample a menu full of delicious surprises. Beautifully appointed, with a choice of distinctive seating areas, the Dormy offers an all-day menu built around modern bar food classics and spicy selections from the restaurant's own tandoor oven. A central open fire and elegant soft furnishings encourage you to linger the whole day through.
With fine views over the 18th holes of both The King's and Queen's courses, The Dormy is perfect for golfers and non-golfers alike.
Opening Times
Monday - Thursday 06.30 - 21.30
Friday, Saturday, Sunday 6.00
Hours may occasionally vary according to demand
UK (Freephone)
0800 731 9219


text:
|Publication number
|Publication type
|Publication date
|Sep 26, 1972
|Filing date
|Nov 9, 1970
|Priority date
|Nov 9, 1970
|Publication number
|Paul Donald G
|Original Assignee
|Chemalytics Corp
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (5), Non-Patent Citations (2), Referenced by (8), Classifications (19)
|External Links: USPTO, USPTO Assignment, Espacenet
United States Patent Paul 1 1 Sept. 26, 1972 [54] GAS ANALYSIS APPARATUS AND METHOD USING PARALLEL GAS DENSITY DETECTORS AND DIFFERENT CARRIER GASES TO DETERMINE MOLECULAR WEIGHT [72] lnventorz' Donald G. Paul, Kennett Square,
[73] Assignee: Chemalytics Corporation, Unionville, Pa.
[22] Filed: Nov. 9, 1970 [21] Appl. No.: 87,680
Parsons, Bracket Method for Molecular Weight Determination of Pyrolysis Products Using Gas Chromatography with a Gas Density Detector, Analytical Chemistry, Vol. 36, No. 9, August, 1964, pp. 1849- 1852.
Lovelock et al., The Palladium Transmodulator: A New Component for the Gas Chromatograph, Analytical Chemistry, Volume 41, No. 8, July, 1969, pp. 1048- 1052.
Primary Examiner-Richard C. Queisser Assistant Examiner-C. E. Snee, lll Attorney-Mortenson and Weigel 57 ABSTRACT A method and apparatus are provided for measurement of a function of the molecular weight of a volatile chemical compound of a sample and the absolute weight contained therein by dividing a flow of volatilized sample into a plurality of portions having a fixed volume proportion to each other, trapping the chemical compound from each of said portions separately in trapping means, transferring the chemical compound of each of said portions into different carrier gases, said carrier gases differing in molecular weight from each other and from the chemical compound of the sample to form separate flows and passing the separate flows through separate means of the recording gas density cell type whereby signal outputs are obtained, the ratio of any two signal outputs being a function of the molecular weight of the compound, the means for trapping of the chemical compound to be measured preferably including a chromatographic tube when more than a single component is present.
13 Claims, 6 Drawing Figures PATENTED SW25 I973 3,693,403
so v 7 52 4a 68 12 0 46 as SFe SP6 N2 N2 FIG. I.
INVENTOR DONALD G. PAUL 8ZMM 'EM7 ATTORNEYS BACKGROUND OF THE INVENTION This invention relates to a method and apparatus for analysis of volatile substances as a function of molecular weight and more particularly to a method and apparatus for direct determination of molecular weight of substances.
It is known to determine molecular weight by the use of a gas density detector cell (gas density balance) in which a ratio of electrical resistance between upper and lower electrical elements varies by heat interchange created from difference of flows of sample, carrier gas and reference gas as measured with a bridge circuit.
This prior art procedure involves programming a flow from a gas chromatography unit to a gas density balance and measuring the electrical resistance as it changes during flow of the sample through the gas density cell. The gas density balance divides a flow of a reference gas into an upper and a lower path the rate of flow of each being measured by electrical detectors. When a sample in the same reference gas as a carrier gas is fed into the cell, a sample of molecular weight (gas density) lower than that of the reference gas rises to the upper path and retards the flow of the upper path and a differential between the electrical output of the detectors is created. Conversely, a sample of molecular weight higher than that of the reference gas falls to the lower path and retards the flow of the lower path so that a differential which is electrically measurable by the output of the detectors is similarly produced. By repeating the process with a second carrier gas different from the first used gas and using identical flow rates in the same apparatus Liberti et al. (atti. accad. nazl. Lincei. Rend. 20,623( 1956) obtained molecular weight results accurate to within 4 percent.
The procedure of Liberti et al. required exact replications of sample weights, identical replication of flow rates, heating temperatures, sample treatment, and recording rate. Moreover, any handling and loss errors were required to be identical. For these reasons, no success in practical use of the procedure for molecular weight determination of unknown samples ever evolved. In spite of the rapid growth in gas chromatography, developments since the discovery of Liberti et al. have always taken paths which required more complicated additional apparatus for qualitative analysis of the sample, such as mass spectrometry, infra-red analysis and the like. Since the retention time of a sample in the chromatographic system does not necessarily deliver components of a sample in order of molecular weight these later developments have not led to a simple method of determination of molecular weight without resort to further analysis.
Now it is an object of the present invention to provide a method and apparatus for the direct determination of the molecular weight of a chemical compound.
It is a further object to provide a method and apparatus for determining the molecular weights of individual components of a chemical mixture.
It is a still further object to provide a method and apparatus for simultaneous determination of retention times and molecular weights of chemical compounds for qualitative analysis thereof.
It is also an object to provide a method and apparatus for determination of both molecular weight and ab- 5 solute weight of individual components of a chemical mixture.
lt is a still further object to provide a method and apparatus for direct determination of molecular weight and/or absolute weight of a chemical compound in a mixture using a single sample and two different carrier gases.
It is yet another object to provide a method and apparatus for determination of the molecular weight of a I a portion of said sample in fixed proportion to the whole; a plurality of trapping means for trapping the chemical compound from each flow and subsequently releasing the compound into a different carrier gas in each trapping means; means for introducing a different carrier gas into each trapping means to form a flow of said compound in the respective different carrier gas; means including a plurality of gas density detectors flowably connected to each trapping means for detection of the chemical compound contained therein and flowably connected to a flow of reference gas of the same chemical composition as the carrier gas containing the sample portion, said gas density detector being capable of providing an electrical signal that varies in accordance with the flow rate of the reference gas and the flow rate of the reference gas as modified by the compound flowing from said trapping means into the detector cell.
These objects are further achieved by the method of dividing a sample containing a chemical compound into a plurality of portions having a fixed quantitative proportion to each other, trapping the chemical compound to be measured from each portion, transferring the compound so separated from each portion into a different carrier gas to form a plurality of flows of the compound in different carrier gases, passing each said flows into a separate signal recording gas density detector in which each gas density detector cell is provided with reference gas of the same composition as the carrier gas and recording the signal output of the detector cells during the period of flow, the ratio of two signal outputs being a function of the molecular weight of the compound.
BRIEF SUMMARY OF THE INVENTION In contrast with the prior art using the gas density detector for qualitative analysis of a volatile chemical compound in gas chromatography apparatus using repeat analyses in two different carrier gases, the present invention provides a method and apparatus for direct determination of both retention time and molecular weight whereby the chemical compounds are analyzed both qualitatively and quantitatively.
In the process of the present invention, the sample containing a chemical compound is divided into a plurality of portions having a fixed quantitative proportion to each other. The chemical compound in each portion is then individually trapped and subsequently transferred separately into different carrier gases so as to provide a pluralityof flows of sample in the different carrier gases. Each flow of the chemical compound in its respective different carrier gas is then passed into a separate signal recording gas density detector of the gas density cell type in which each gas density cell is provided with a flow of reference gas of the same composition as the carrier gas in the sample flow. The signal output of the detector cells is recorded during the period of flow so as to form at least two curves, the ratio of the areas under which is a function of the molecular weight of the chemical compound.
The sample is usually divided into two portions which are treated similarly in two different carrier gases, but there are advantages in analysis using division into three or four portions and treating similarly in different carrier gases.
The carrier gases are substances differing in composition and molecular weight from the compounds in the sample to be analyzed. The carrier gases used are usually single component compounds which pass through the apparatus without change in composition. One carrier gas preferably is of higher molecular weight than the compound of the sample to be analyzed and the other is preferably of lower molecular weight than the compound of the sample to be analyzed. The carrier gases which are useful are chemical elements or compounds having molecular weights from 2 to 200 and even higher by using suitably high temperatures in the apparatus. Examples are: hydrogen, helium, argon, neon, krypton, nitrogen, carbon dioxide, carbon tetrafiuoride, chlorotrifluoromethane, bromotrifluoromethane, dichlorodifluoromethane, trichlorofluoroethane, perfluoropropane (C F sulfurhexafluoride (SF octafiuorocyclobutane and 1,1- difluoroethane. Hydrogen is rarely used because of its reactivity and possible explosion hazard. It is usually desirable to use compounds of purity better than 99 percent. Helium, nitrogen, or carbon dioxide is quite satisfactory for use as the low molecular weight carrier gas and sulfur hexafluoride or octafluorocyclobutane as the high molecular weight carrier gas.
The chemical compound of each sample flow is trapped in a trapping means described hereinafter. When the sample to be analyzed contains a single compound, the trap is a simple means for condensing or adsorbing the compound on the surface area of the trap. The atmosphere of the trap is then replaced by carrier gas and the sample is transferred into the carrier gas by heating the trap while flowing carrier gas through the trap to produce a flow of the compound in the carrier gas.
When the sample contains more than a single compound the trapping means is a two-stage trapping means and the mixture of compounds which are components of the sample is first trapped by a simple trap in the first stage and the mixture is transferred into the carrier gas by heating the trap while flowing carrier gas through the first stage trap to produce a flow of the mixture in carrier gas. The flow of mixture in the carrier gas is then passed into and through a chromatographic tube where there is a difference in retention times for the individual chemical compound components and, as a result, effluent from the chromatographic tube is a series of flows. Each flow of the series contains a single chemical compound in the carrier gas, the flows being in the relative order of their respective retention times.
Generally, the chromatographic tubes for the plurality of flows are substantially identical as to the retention properties. However, there are advantages in having them different so as to have different retention times. The retention times and molecular weights taken together are useful in identification as to chemical structure.
BRIEF DESCRIPTION OF THE DRAWINGS The apparatus of the invention is briefly described for simplicity showing apparatus for dividing a sample into a pair of flows in two different carrier gases. It is to be understood that apparatus for dividing the sample into a plurality of flows in which three different carrier gases are used requires a divider for splitting the sample into three flows and three trapping means and three detectors similar to the diagrams wherein only two flows are shown.
FIG. 1 is a diagram of a complete apparatus provided in accordance with the invention with a showing of the routing of flows in a first step of procedure.
FIG. 2 is a view similar to FIG. 1 but showing a second step of procedure with omission of portions of the apparatus irrelevant to that step;
FIG. 3 is a view similar to FIG. 1 but showing a third step of procedure with irrelevant portions of the apparatus omitted;
FIG. 4 is a view similar to FIG. 1 but showing a fourth step of procedure with irrelevant portions of the apparatus omitted;
FIG. 5 is a diagram of a pair of records produced by recorders and which are to be compared;
FIG. 6 consists of the more important equations explanatory of the theory and practice of operation.
DETAILED DESCRIPTION FIG. 1 shows the apparatus as a whole, indicating the routing of flow in the first step of operation. Where valves are indicated, it is understood that many of these are used in ganged combination so that the control of one simultaneously controls another in the gang.
Describing first a particular construction, an inlet 2 may serve for the introduction, from a source under pressure, of a carrying gas which may be of any suitable type into which there is subsequently introduced the sample for which analysis is desired. This connection runs to a splitter tee 4 to provide division of flow through fiow restrictors 7 and 9, into conduits 6 and 8, respectively, which restrictors may be physically provided by capillary tubing which need not be exactly matched in size and length. The reason for these restrictors, functioning like high electrical resistors, is to provide a reproducible division of two high speed flows essentially independent of variations in conditions beyond the conduits 6 and 8 which might affect the division of flow. For example, as will presently appear, the flows run to traps, changes of temperature of which, or changes of other conditions of which, can change the ratio of the respective flows, whereas if sufficient resistances are interposed by restrictors 7 and 9 the disturbances downstream will have negligible effect. ln addition, the resistances essentially eliminate any gravitational effects, the resistors giving rise to high linear rates of flow proportional to pressures at the tee 4 due primarily to accelerations. The respective flows need not be equal; in fact, in many instances inequality will produce better results in view of different conditions in later parts of the apparatus and their operations. What is required is a nearly fixed ratio of the two flows so that results obtained in the handling of unknowns will be comparable with the handling of known materials during calibration.
The gas introduced at connection 2 may be provided from a supply bottle under pressure with regulation of rate of flow through a flow regulator 10 which, like other regulators hereafter described may be of the wellknown type commonly used in gas chromatography. Beyond the flow regulator, there is a sample port 12 for introduction of solid, liquid or gaseous sample in conventional fashion. This injection port is preferably suitably heated so that the injected sample will be vaporized so as to be carried by the gas. It is desirable that immediately following the injection port there should be an enlarged chamber 13 to prevent an undue rise of pressure caused by sudden vaporization of the sample, better uniformity of the division being obtained when the pressure at the tee 4 remains approximately constant. Such a chamber is particularly desirable since the conventional regulator present at It) usually has a rather slow response.
The dividers, capillary tubing, chromatograph tubes, gas density cells, valves and other parts of the apparatus may be made of glass, metal such as stainless steel, plastic or other material selected to be suitable for the particular samples and carrier gases used.
The foregoing describes a particular arrangement and operation in which the carrying gas is at an elevated pressure and the sample is injected beyond a regulator. However, the sample may be present in the carrying gas as it enters at 12, for example, if there is being analyzed a sample gas containing impurities, e.g. polluted air. While for consistency of description there will be referred to entry of gases under pressure, it will be evident that all that is required is a pressure gradient or gradients to produce flow, and consequently flow may be provided by the application of suction to various points which are referred to hereinafter as vents, with input at any desired pressure, for example atmospheric if contents of air are to be analyzed.
While the use of gas to carry the sample through the restrictive divider capillary tubes 7 and 9 is convenient and practical, it is to be understood that there are also advantages to the application of a suction in the flow lines to be described hereinafter for drawing the vaporized sample into the system through these capillary tubes.
The carrying gas for conveying the sample through the first part of the system up to the step of trapping the two portions of sample in their respective traps is not normally critical as to purity, since it is displaced subsequently by substantially pure carrier gases used for transferring the two portions of sample from their respective traps to the chromatographic separators. The substantially pure carrier gases used in this second step are selected from the gases known in the art and particularly those listed in the description of the method as described above.
The apparatus includes as components various valves which are manually set to selected positions, and those valves are most effectively shown by way of disclosure of their ports in the drawings, with indication in solid lines of connections which exist during the several steps in the operation, while in FIG. 1 alternative connections, not used in the initial step, are indicated in dotted lines. The physical valves themselves are not detailed since they are of conventional types and readily available.
The conduit 6 runs to valve 14 which, in the initial step, provides flow to valve 16 and thence to valves 18 and 20 and from valve 20 into trapping column 22. The valves are selectively operated or ganged where this is convenient and possible, so as to control the flow of gases as desired.
The apparatus is essentially symmetrical, and flow takes place from conduit 8 through the valves 24, 26, 28 and 36) into trapping column 32.
The right hand side of FIG. 1 shows valving which includes valves 34 and 36 and the left hand shows valving which includes valves 38 and 40 which are not utilized in the initial step of operation. The valves 34 and 38 are connected to respective vents 42 and 44.
At 46 there is an inlet connection which, for consistency of description may be said to receive a carrier gas such as nitrogen under pressure, the flow of which gas is controlled by a conventional regulator 48, so that the gas under controlled flow passes to valve 36 in a subsequent stage of operation. In similar fashion an inlet 50 is provided and connected to a pressure source of another gas which for consistency of description may be considered to be sulfurhexafluoride (SF the flow of which is regulated by a regulator 52 from which a conduit runs to the valve 40. The gases nitrogen and sulfurhexafluoride serve in many instances as suitable carriers, the nitrogen having a molecular weight which is low and generally less than the molecular weights of the components of the samples, while the sulfurhexafluoride has a high molecular weight which is often greater than the molecular weights of the components of the samples and is of quite general utility because of its inertness and its high molecular weight.
The lower end of trapping column 22 is connected to a valve 54 to control flow either to a valve 56 which is connected to a vent, or to provide flow to another valve 58.
On the other side of the apparatus the lower end of the trapping column 32 is connected to a valve 60 which provides connection to a venting valve 62 or alternatively to a valve 64.
When the sample is drawn through the divider capillaries 7 and 9 by suction as described above, venting valves 56 and 62 are attached to a suction means such as a vacuum line so as to draw sample portions into the traps.
An inlet 66 connected to a source of nitrogen under pressure provides a flow of nitrogen through a flow regulator 68 and an auxiliary injection port 70 to the valve 58. in similar fashion an inlet 72 connected to a source of sulfurhexafluoride under pressure provides a flow of sulfurhexafluoride through a flow regulator 74 and thence through an auxiliary injection port 75 to the valve 64.
The auxiliary sample injection ports 70 and 75 are provided for the injection of known samples for calibration purposes as well as for quantitative analysis.
These ports are used, for example, when samples are analyzed quantitatively for components of known molecular weights. In such qualitative analysis it is necessary to use only one side of the equipment and only one carrier gas. In this case the carrier gas which gives the largest response is used. Thus, it is advantageous to use the high molecular weight carrier gas such as sulfurhexafluoride in analyzing low molecular weight components and the low molecular weight carrier gas such as nitrogen or helium in analyzing high molecular weight components.
A valve 76 is connected to the lower end of a gas chromatograph column 78, while a corresponding valve 80 on the other side of the apparatus is connected to the lower end of a gas chromatograph column 82.
At this point it may be remarked that while, for simplicity of disclosure, multiple inlet connections to pressure sources of nitrogen and sulfurhexafluoride are indicated, and will be further indicated, these connections may be made to the same supplies of the respective gases and the several flow regulators may in some instances be the same regulators when they are not required to operate simultaneously, the routing of the gases being provided by suitable valving as will be obvious. Close-off valves, not known, are provided to open and shut inlets in obvious fashion at the sources.
Symmetrically provided in the apparatus are detectors such as density meters 84 and 86 which are of a well-known type described in detail in US. Pat. No. 3,050,984, dated Aug. 28, 1962, and elsewhere.
Each of the detectors 84 and 86 is of the type in which vertical passages are provided which have reception zones at their respective mid portions for reception of reference gas and for reception of the same gas carrying a sample. The reference gas passes in heat conductive relation with a pair of thermally responsive electrical detectors connected in a bridge circuit providing an output to a recorder which is part of each detector (though a dual recorder may serve for both) and not known per se. The gas containing the sample controls the flows of the reference gas by becoming admixed with the flowing reference gas, and the combined gases pass to a vertically centered outlet. The conduits connected to other apparatus are as follows:
The conduit 88 runs from the upper end of the column 78 to the mid portion of a vertical passage 89 in the detector 84, and in similar fashion a conduit 90 runs from the upper end of column 82 to the mid portion of a vertical passage 91 in the detector 86. An inlet 92 connected to a pressure source of nitrogen runs through flow regulator 94 and then through conduit 96 to the mid portion of the vertical passage 97 at the upper and lower ends of which connections are made to horizontally running extensions of the upper and lower ends of the passage 89. The flows unite and the combined discharge passes through the outlet conduit 99. This outlet may either be a vent, or it may be a conduit leading to a trapping column in the event the sample is to be retained for some further operation.
In similar fashion an inlet 98 connected to a pressure source of sulfurhexafluoride runs to a flow regulator 100 and thence through conduit 102 to the mid portion of the vertical passage 103, which corresponds to 97. The flow passages are similar to those previously described, outlet flow taking place through the conduit 105.
Indicated in the detector 84 are the respective upper and lower elements such as thermally-responsive elements 104 and 106, such as filaments or thermistors, while corresponding elements are designated 108 and 110 in the detector 86. The operation of the detectors is a conventional one in which variations in the upward and downward flows of the reference gases produce electrical unbalance of the thermally-responsive elements so as to provide operation of the corresponding recorder.
The various trapping columns 22 and 32, chromatographic columns 78 and 82, and detectors 84 and 86 are provided with heaters which are indicated in FIG. 1 at I-I to H, inclusive. These heaters for the absorption columns and the density detectors are arranged to provide proper temperatures, thermostatically controlled, at various stages of the operation not only to these major components but also to connecting conduits with the objective of maintaining thermal stability, and in the case of the absorbing columns, also to provide conditions for holding and vaporization of the sample material. The temperatures maintained are, of course, selected to suit the particular materials which are involved.
For the same purpose and also to maintain gas compositions constant, except when intentionally changed, flows of carrier gases are maintained in all parts of the system whether actively involved in carrying out the individual steps of operation or not.
Reference may now be made to the operational steps in making a quantitative analysis of the constituents including their identification by their molecular weights in apparatus which has been calibrated and is ready for use. The operations will be first described without reference to theory.
FIG. 1 indicates in full lines the connections which are involved in the initial part of the operation which effects a division of a sample to be analyzed into two definitely related portions. In this initial phase of operation the trap heaters are ordinarily off (or at low heat) with the trapping columns 22 and 32, particularly at room or other low temperature, although if highly volatile materials are contained in the sample these may even be subjected to refrigeration. Assuming, for
generality, that the carrier gas in the introduction step,
is a gas other than nitrogen or sulfurhexafluoride, it is desirable, in order to secure definiteness of division of the sample, when using a carrier gas before division, to have the carrier gas flow for a period preceding the sample introduction so as to secure uniformity of gas content particularly in the columns 22 and 32. Following this, an operable quantity of the sample is introduced into the injection port 12 while the gas is flowing from the inlet 2 and while heating the injection port 12, if necessary to maintain volatility, so as to accelerate vaporization of the sample. Definite division of the samples takes place at the splitter tee 4 from which the split flows are led to the columns 22 and 32.
The columns 22 and 32 are high surface chambers and usually contain an adsorbing material such as any of a great variety of adsorbing materials well-known in the art of gas chromatography, for example: Alumina, silica, clay, metal silicates, acrylic polymer beads, Apiezon L, Carbowax M, Silicone OV- 7, Squalane, Poropak P, Q, R, S, or T, glass beads, Teflon, activated charcoal, or mixtures. Various of those listed are proprietary products, sold under trademarks. The actions involved are essentially physical, and in the adsorption the action is in many cases essentially condensation, either on more or less inert porous material or in viscous liquid or semi-liquid coatings on inert carriers, or true molecular adsorption. The action involved in removal of the constituents is the reverse, i.e., essentially vaporization. Chemical reaction is not usually involved; and as will be pointed out later, the order of desorption that occurs is not entirely a-function of molecular weight, or of chemical composition.
The adsorbing materials such as those just indicated have the property, when cold, of very quickly adsorbing the sample constituents from the influent gas with the desirable result that for all intents and purposed the entire content of the sample is held at the upper ends of these columns. It is not desirable at this stage to have the adsorption take place in a chromatographic fashion, i.e., distributed along the column, but rather the adsorption is desirably in small slugs occupying little of the column length with the ultimate objective of providing a compact source from which the sample materials in the two columns may be practically simultaneously and in a very short period driven off with heat and delivered into the chromatograph columns 78 and 82, thus increasing column efficiency.
At the time this sample-depositing step is carried out,
it is convenient to prepare other portions of the apparatus for use, although this is merely a cleaning and stabilizing operation, by causing nitrogen to enter at inlet 66 and to pass into the bottom of column 78 and from it through conduit 88 to sweep through the passages in the detector 84 which also receives nitrogen from the inlet 92. A similar cleansing and stabilizing operation is carried out through the corresponding elements in the left hand portion of the apparatus by introducing sulfurhexafluoride at the inlets 72 and 98.
The second step in the operation is illustrated in FIG. 2 which, for simplicity, omits those elements of the apparatus which are not involved in this step, the auxiliary injection ports 70 and 75 being also omitted, though flow takes place therethrough, and also through the other passages to maintain stabilization.
The purpose of the second step is to replace in the columns 22 and 32 the carrying gas which was used to introduce the samples by, respectively, nitrogen and sulfur hexafluoride. One of these gases is suitably al ready in its proper half of the system if the same gas had been used originally by introduction at inlet 2. in the right hand portion of the apparatus, nitrogen is introduced at 46 and flows through the conduits illustrated downwardly through the column 22 (which remains cold) with venting at 56. In similar fashion sulfurhexafluoride introduced at 50 passes downwardly through the column 32. Theseoperations are carried out sufficiently to insure that the two portions of the apparatus contain as gases the nitrogen and sulfurhexafluoride respectively. The conduit and valve connections to columns 78 and 82 and to the detectors 84 and 86 are the same as illustrated and described with reference to FIG. 1.
While the second step just described is desirable, and in some cases necessary, depending upon the carrier gases and the composition to be analyzed, in other instances this step may be omitted and when this is the case there may be corresponding simplification of the apparatus particularly in the matter of the valve connections preceding the trapping columns. Hence the described second step is not of the essence of the procedure.
The nest step is illustrated in FIG. 3, from which irrelevant portions of the apparatus are omitted, (though flows may continue for stabilizing as mentioned) and involves the purging of the samples from the trapping columns 22 and 32 into the chromatograph columns 78 and 82. The former are now heated and the latter remain cool, or are adjusted to a lower temperature than the trapping columns as necessary to get optimum absorption conditions. Nitrogen introduced at 66 is routed through the regulator into the lower end of column 22 and from which it removes the slug of sample and introduces it into the chromatograph column 78. In this last column, the stratification occurs in which the more volatile components of the sample usually become located higher in the column than the less volatile components. Nitrogen freed from the components now located in the column 78, flows outwardly and may be conveniently routed as indicated through the passages in the detector 84. Similar operations, effected by sulfurhexafluoride entering at 72 take place, displacing the slug of sample from column 32 into the chromatograph column 82, the former being heated and the latter remaining cool or being cooled or heated at a lower temperature.
The columns 78 and 82 suitably contain chromatographic absorbing material of any of a wide variety of types, and these materials may be the same as those previously described as used in the trapping column. From the many column fillers which are available choices may be made of those giving best results for particular classes of materials and carriers, though little differences are noted in comparing the operations of different adsorbing materials. Controlled temperatures are selected to secure optimum results. A trapping" action may be produced at lower temperatures whereas at higher temperatures better stratification may occur, with separation of the components rather than their accumulation in limited slugs. The separation effective in these columns provides for the later introduction into the detectors of the sample components in a sequence beginning with the most volatile and ending with the least volatile.
The final step'of operation is illustrated in FIG. 4, there being here omitted, as before, the irrelevant portions of the apparatus through which flows continue, as stated. What is carried out in this final step is the displacement of the sample components, beginning with the most volatile into and through the detectors to pro vide records; Nitrogen introduced at 66 has its rate of flow'controlled by regulator 68 and enters the column 78 to displace the sample components through the detector 84. The column 78 is heated to a temperature suitable for the components involved and the ambient temperature of the detector 84 is also maintained constant and also at a suitable value. The detector now operates in conventional fashion, reference nitrogen being introduced at a regulated flow rate through the connection 92 and the flow regulator 94. As is known for this type of detector, the relative densities of the twoflows now come into play so that the rates of flow of the reference nitrogen past the elements 104 and 106 create unbalance of the electrical bridge which is recorded. The same type of operation occurs in the left hand portion of the apparatus, except that sulfurhexafluoride now constitutes the displacing gas and also the reference gas. There is, of course, a reversal of the conditions involved in that the reference nitrogen would have a lower density than nitrogen containing the components heavier than it, while the reference sulfurhexafluoride would have a greater density than the portions of sulfurhexafluoride containing the sample components lighter than it. This fourth step of programmed elution to detectors using the nitrogen and sulfurhexafluoride carrier gases may be carried out either simultaneously or successively, the same electrical recorder being possibly used in the latter instance.
When a single component sample is being analyzed, it is possible to use only the first named traps by making the exchange to pure carrier gas therein and then heating the traps so as to form an admixture with the carrier gas so as to create flows which carry the sample in pure carrier gas directly to the gas density cells. The sample in the trap is allowed to flow from either its inlet end or from its outlet end directly to the gas density cells. This procedure differs from the base in which the gas is passed to chromatographic tubes for separation of a multicomponent sample, in that a multicomponent sample is preferably allowed to pass from the first named trap through the inlet end by reversal of gas flow. The reason for removal from the trap by reversal of flow is so that no separation of sample takes place prior to the development of separation in the chromatographic tubes.
The advantages of the apparatus and procedure of the present invention will now be clear. The sample is divided into two portions being a known quantitative relationship to each other and are handled in substantially identical fashions. Any difference in handling, due to the use of the two carrying gases, is constant from run to run, and from the standpoint of the production of the density records the result achieved in each recorder is the same resulting in direct comparison so that in the two records the components can be easily identified. As is well know, the quantitative amount (weight) of a constituent is determined by the area of the peak produced in the recorder chart as compared to an area produced by a standard sample. With proper rates of flow through the chromatograph columns, the records consist of a constant baseline graph (resulting when the components are not passing through the detector) with peaks occurring whenever the components are passing. The sequence of the peaks and their spacings can be recognized as definitive of the components. This recognition, of course, is afforded particularly by calibration. The calibration is carried out by the introduction of known samples at the auxiliary injection ports and 75, the nitrogen and sulfurhexafluoride being introduced at controlled rates first to build up the array of the components in the chromatograph columns 78 and 82 and then to transfer them serially through the respective detectors to give basic graphs corresponding thereto. Maintenance of constant chosen conditions makes the results comparable so as to achieve high accuracy of identification and measurements.
Under some conditions simplifying variations of the apparatus may be used, For example, it is possible that the trapping columns 22 and 32 may be bypassed by introduction of the sample in the two flows directly into the chromatograph columns 78 and 82 through injection ports 70 and 75. However, it is more generally desirable to utilize the trapping columns 22 and 32 to accumulate first slugs of the divided sample, thus to avoid such differences as might arise from the direct introduction which introduces added error not involved in the usual injection and splitting procedure above described. The slug accumulation on the traps, without any substantial separation of constituents, permits the further operations to be carried out simultaneously under simultaneously existing conditions as to temperature, pressure and flow rates.
With proper precautions and added valving for gas purging and introduction of another gas, a single detector may, of course, be used.
FIG. 5 shows two graphs G and G, which are the comparable graphs produced by the recorders operated by the signal outputs of the gas density cells. Each consists of a number of peaks, and under normal conditions of simultaneously feeding the series of flows from the chromatographic columns to the detectors,
the sequences of the peaks on the two graphs produced A will correspond, i.e., peaks which are produced at corresponding positions in the two sequences such as P and P,, represent the measurements of the same component of an unknown (or of a known substance in calibration). The relative areas of these peaks are of consequence and are determined by the use of a planimeter or graphically, or by electronic integrator.
The operation of a density measuring cell, arbitrarily referring to one of the pair shown, produces data which are related in accordance with equation (1) of FIG. 6, in which:
W is the actual weight of a particular component of the unknown sample producing a single peak in passing through the cell;
A is the corresponding area of the single peak in the graph of the response of that cell to the passage of that component;
K is the cell constant;
M, is the molecular weight of the carrier gas used for carrying that component through the cell, and also used as a reference gas.
M is the molecular weight of the carrier gas used for carrying that component through the cell, and also used as a reference gas.
Likewise the corresponding relation of data for the second cell is given in equation (2) of FIG. 6 in which:
W, is the actual weight of a particular component of the unknown sample producing a single peak;
A, is the corresponding area of the single peak in the graph of the response of that cell to the passage of that component;
K, is the cell element constant which is separately determined M I is the molecular weight of that component which produces the peak, and
M is the molecular weight of the second carrier gas used in that cell.
Since the total weight of the component, W, is the sum of W, and W and W, and W, are related according to the splitting ratio a, a
and from this the expression (3) and (4) follow:
By substituting (l) in expression (3), and (2) in expression (4) there is obtained equation (5) in which (k,)/(k,) (a,)/( a K.
K is thus a constant for the apparatus which is determined by passing any known pure sample through the analytical process. Normal heptane is a satisfactory pure material which can be used for this purpose. When K is substituted for (kg/(K a )/(a,) in equation (5 the following equation is obtained.
By designating K (Ag/(A to be a constant Y,
and YM, YM,,, M M which by rearranging becomes YM M YM M or (Y -l) M,
YM which on dividing by (Y 1) becomes equation (7) After solving for K using a known pure compound as indicated above and using one gas, Y can be similarly found by repeating the process with a pure compound weight of the sample is calculated. If there are several components in a sample resulting in several peaks the equation can be set up in a computer so that only the ratio AJA, for each component needs to be changed for each molecular weight determination of the several components.
It is to be noted that when calibrating the apparatus with a pure sample, the pure sample should be one with a molecular weight greater than that of the carrier gas used so as to correct for the slight difference which may occur between pairs of gas density cell thermally responsive resistors.
The apparatus of this invention provides a simultaneous measurement of two portions of a sample whereby errors due to fluctuations in temperatures, flow rates, and pressures cancel out, and the constants determined for the apparatus and used in the calculations are fixed. Moreover, the apparatus using the splitter and plural flow system provides easy and accurate control of heating and cooling, as required, in such a manner that a true comparison of the two portions of split sample is obtained. As a result, accurate measurement of molecular weight of sample components is readily achieved.
While it is possible to use apparatus according to the present invention comprising a sample splitter, a plurality of traps, including when desired, a simple trap and chromatographic tube trap in series and then not a plurality but a single gas detector cell to analyze first the sample in one trap in one carrier gas and then a sample in another trap in a different carrier gas and thus simplify the apparatus, such apparatus has one of the serious disadvantages of the prior art, namely, the time required to thoroughly clean the first carrier gas from the detectors system before using it for the second different carrier gas. The present invention using a plurality of gas detectors overcomes this disadvantage. The present invention does not, however, exclude the non-simultaneous analysis of the flows from the trap systems whereby a single recorder can be used first for recording peaks of one flow and then recording peaks of a second flow. Such a system is useful when using for example three chromatograph flows and only one dual pen recorder.
It is obvious that the process of this invention is not limited to the division of a flow of gas into two samples portions and comparison of the sample in two different gases, since additional sample portions can be compared in a third and even a fourth different gas for greater accuracy. Furthermore, columns with different packing materials can be used and this is particularly advantageous when a third and a fourth portion in a third and fourth different additional gas is used. The data therefrom will provide greater accuracy and precision in identifying components of complex mixtures. When quantitative analysis is desired, the apparatus is calibrated with a known weight of a known compound, and the molecular weight and absolute weight of one component of the sample injected must be known. In the case of an unknown sample, a known percent of a known compound can be mixed with the sample to produce a sample for this purpose.
The above description applies more particularly to qualitative analysis. The formulas given above are used 'in this calculation, e.g., M
---- II Alan In the first calculation, k is calculated using a known weight of the known sample t of known molecular weight M and known molecular weight of carrier gas M to obtain the area A,. Then this k is used in the same formula where t M, and A, are respectively weight, molecular weight and area under the curve for the unknown in the sample.
What is claimed is:
1. Apparatus for measurement of a function of the molecular weight of a volatile component of a sample comprising: I
a. means for dividing a flow of sample containing a chemical compound into a'plurality of flows each containing a portion of said sample in a fixed proportion to each other;
. separate trapping means disposed in each of said flows for separating and releasing each of said chemical compound portions from its respective flow,
c. means associated with each of said trapping means for entraining the respective separated chemical compound portions in different flows each of a different carrier gas;
. detector means including a plurality of gas density detector cells capable of providing an electrical signal that varies in accordance with the difference in flow rates of a reference gas and said reference gas modified by a content of a compound of different molecular weight, said detector cells being provided with a reference gas inlet and a sample gas inlet, said sample gas inlet being flowably connected with its respective trapping means.
2. Apparatus of claim 1 in which the sample dividing means is a means for dividing the sample into a plurality of flows not exceeding four.
3. Apparatus of claim 2 in which the sample dividing means is a means for dividing the sample into a pair of flows.
4. Apparatus of claim 3 in which each trapping means is heat controlled and is a high surface area vessel having substantially no differential retention properties.
5. Apparatus of claim 3 in which each trapping means is a two stage trapping means wherein the first stage includes means for transferring a plurality of chemical compound components from each sample flow as a mixture into a carrier gas and the second stage includes means for separating chromatographically said plurality of chemical compound components into a series of flows of individual chemical compounds in the respective carrier gas.
6. Apparatus of claim 5 in which the two stage trapping means includes a first stage trapping means having substantially no differential retention properties for entraining the respective separated chemical portions and a second, stage trapping means having substantial differential retention properties and valving means therebetween whereby flow from the first stage trapping means to the second stage trapping means is controlled.
7. A method for measurement of the molecular weight of a volatile chemical compound component of a sample comprising: chemical compound into a plurality of flows of portions having a fixed quantitative ratio to each other;
a. simultaneously dividing a sample containing a chemical compound into a plurality of flows of I portions having a fixed quantitative ratio to each other;
b. simultaneously trapping the chemical compound from each of said portions and simultaneously transferring said chemical compound of each of said portions into a different carrier gas to form a plurality of sample flows in respective different carrier gases;
c. simultaneously passing each said flow into a separate signal recording gas density detector of the gas density. cell type in which each gas density cell is provided with a flow reference gas of the same composition as the carrier gas in the sample flow; and
. simultaneously recording the signal outputs of the detector cells during the period of flow, said signal outputs being a function of the molecular weight of said chemical compound.
8. The method of claim 7 in which the sample consists of an individual chemical compound in a carrier gas and steps b and c comprise the steps of trapping each chemical compound, purging the carrier gas therefrom with said different carrier gas and detrapping each chemical compound into its respective different carrier gas.
9. The method of claim 7 in which the plurality of sample portions does not exceed four.
10. The method of claim 9 in which the sample is transferred into a first carrier gas of different chemical structure than the chemical compound component of the sample to be measured to form a sample flow and the sample flow is divided into a plurality of sample flows, from which flows each compound component is subsequently separated from thefirst carrier gas before different carrier gases, each flow comprising a flow of g the chemical compound component in the respective carrier gas serially separated from each other in order of the chromatographic retention time of each chemical compound.
12. The method of claim 11 in which the chemical components of the mixtures in difierent carrier gases are chromatographically separated on chromotographic columns having different adsorbent properties so as to provide a plurality of flows in which the retention times are different in each flow.
13. The method of claim 12 in which both retention time and molecular weight are determined from the data as a means of chemical identification.
|Cited Patent
|Filing date
|Publication date
|Sep 13, 1965
|Dec 5, 1967
|Shell Oil Co
|Chromatographic analysis
|Nov 16, 1964
|May 28, 1968
|Phillips Petroleum Co
|Chromatographic analyzer
|Jun 22, 1966
|Nov 5, 1968
|Phillips Petroleum Co
|Gas chromatography sensing means
|Oct 23, 1968
|Dec 8, 1970
|Hewlett Packard Co
|Method and apparatus for determining the molecular weight of volatile compounds
|Oct 22, 1965
|Jun 15, 1971
|Sinclair Research Inc
|Fluid analysis by gas chromatography employing multiple carrier gases and multiple columns
|Lovelock et al., The Palladium Transmodulator: A New Component for the Gas Chromatograph, Analytical Chemistry, Volume 41, No. 8, July, 1969, pp. 1048 1052.
|Parsons, Bracket Method for Molecular Weight Determination of Pyrolysis Products Using Gas Chromatography with a Gas Density Detector, Analytical Chemistry, Vol. 36, No. 9, August, 1964, pp. 1849 1852.
|Citing Patent
|Filing date
|Publication date
|Nov 13, 1978
|Dec 25, 1979
|Envirochem Inc.
|Isolation and concentration of sample prior to analysis thereof
|Mar 6, 1986
|Jul 7, 1987
|Precision Measurement, Inc.
|Method and apparatus for measuring the relative density of gases
|Jan 1, 1995
|Jun 11, 1996
|Haskell; Weston W.
|Gas chromatograph flow calibrator
|Jun 19, 2007
|Jun 22, 2010
|Seer Technology, Inc.
|Apparatus, system, and method for broad spectrum chemical detection
|Jun 19, 2007
|Oct 5, 2010
|Seer Technology, Inc.
|Apparatus, system, and method for improved power utilization in a gas chromatography sensor
|Jun 19, 2007
|Jan 10, 2008
|Gary Bodily
|Apparatus, system, and method for broad spectrum chemical detection
|Jun 19, 2007
|May 8, 2008
|Arnold Neil S
|Apparatus, system, and method for improved power utilization in a gas chromatography sensor
|Jun 20, 2007
|Dec 24, 2008
|Neal Arnold
|Apparatus, system, and method for improved power utilization in a gas chromatography sensor
|U.S. Classification
|73/23.35, 73/23.4
|International Classification
|Cooperative Classification
|European Classification

subset: commoncrawl


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Earlier this year we asked our Members to send in examples of colourful, insulting and threatening language directed at them or their fellow officers during the course of their duties. We received a ... Read more
The WA Police Union has rejected the State Government's miserly pay offer on behalf of the State's police auxiliary officers. The Government's offer was a 1.5 per cent pay rise per year for two years ... Read more
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The battle to get compensation for paralysed police officer Ryan Marron is still ongoing. Nearly five years after contracting Murray Valley Encephalitis, Ryan's legal team and the WA Police Union are ... Read more


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Brewers Festival sells out in 11 minutesMay 17,2014Brewers Festival
sells out quickly
The Associated Press
BURLINGTON Thinking about going to the Vermont Brewers Festival on the Burlington waterfront this summer? You might be out of luck. A festival producer says tickets sold out in 11 minutes for the 22nd annual event on July 18 and 19.
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Latest articles from the Biofortified Blog
Give Silenced Crops your Voice!
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Turkey Feathers: Pattern
Students express what they are thankful for using this turkey and feather pattern. See Full Product Description.
Grade: PreK - 3 Theme: November, Autumn Themes, Thanksgiving Type: Cut and Pastes File Size: 163 KB
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Students express what they are thankful for using this turkey and feather. Pattern includes a turkey's body with a line for student's name and a feather pattern entitled, I'm thankful for.... Make multiple copies of feather pattern and have students glue them to the turkey's body.
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Display turkeys on the class bulletin board. Student can add the I'm thankful for...feathers to their own turkey! Students can also write the name of a family member in the center of the turkey. Then on the feathers write what they are thankful for about.


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My PNG transparent images have gray backgrounds in IE6 does anyone know how to fix this? Should I use .gif?
My PNG transparent images have gray backgrounds in IE6 does anyone know how to fix this? Should I use .gif?
You don't have to revert to GIFs. You'll have to use a little bit of JavaScript to get alpha-channel transparency (the kind PNGs use) to work in IE6.
I saw some stuff about that but what if a visitor has java turned off, is there a work around for that? Thank you by the way for replying, I will use this method unless there is a better way to cover all possibilities.
Negative. If a user has JavaScript turned off, then you're SOL.
The script works well but isn't totally foolproof, either. I tried to use it recently when making a faux column layout in conjunction with a sticky footer, and the background image I had applied to #wrap and repeated vertically ran over the footer. So in that case I made a special background image for IE6, without the transparency, and resorted to good ol' conditional comments:
andCode:<!--[if lte IE 6]> <link rel="stylesheet" href="css/ie6.css" type="text/css" /> <![endif]-->
It's not ideal but the visual difference isn't glaringly obvious. It's a judgment call.Code:#wrap { background:url("../images/wrap_bg2ie.png") repeat-y; }


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by Lauren C. Williams Sep 19, 2015
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Poe first proposed this bill just two days after the attack on French satirical magazine Charlie Hebdo.
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Afghanistan's effort to confiscate and destroy toy guns seems misplaced, given that thousands of actual weapons are unaccounted for in the country.
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Abdulazeez did not regularly attend mosque and his alcohol and drug abuse do not align with the behaviors of a religious fundamentalist.
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The regularity of warnings that come to nothing threatens what the Soufan Group described in their July 7 Intel Brief as "Crying Wolf In Terrorism."
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...if the poll is broken down by race, 55 percent of black Americans believe that Roof's actions deserved the terrorism label as opposed to just 37 percent of white Americans.
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Tech companies aren't exactly thrilled about snooping user content for potential terror threats.
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"We're gonna be carrying an M4 with 500 rounds of ammunition, light armor piercing"
by Justin Salhani Jul 2, 2015
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Track Listings
|1. Part One - Mike Oldfield
|2. Part Two - Mike Oldfield
Product Description
Product Description
2009 digitally remastered edition of the British guitarist's musical masterpiece. Fans old and new can celebrate the great work of Mike Oldfield with this very special release of his classic, multi- platinum selling album Tubular Bells. This exciting new version of his 1973 groundbreaking album will not only be repackaged, but Mike Oldfield himself has also remastered the tracks from his home in the Bahamas and has overseen a new stereo mix. This is the first classic album to be released from Mike Oldfield's back catalogue. It is 35 years since the opening passage was used in the film The Exorcist, making the album a global phenomenon. Five tracks.
The opening bars of this classic album by Mike Oldfield were heard by audiences that packed theatres to witness one of the scariest films of all time--The Exorcist. And it wasn't long before this debut release, not only from Oldfield but also from Richard Branson's new record label, Virgin, found itself in the upper echelons of pop charts around the world. Primarily an instrumental album, with performances on almost every instrument credited to Oldfield, it takes the listener into widely varying musical territories, ending as Viv Stanshall formally announces each instrument as it joins the mix. --Paul Clark
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Top Customer Reviews
The first part is the Exorcist theme we all know and love, but there's way more to it than that. I actually prefer the second movement to the first, because it builds nicely and features the most beautiful music I have ever heard. The part I'm talking about is the after the wierd cookie-monster death metal vocal part, at about 16:30, before the Irish pub music. Whenever I hear that part it seriously takes me away to somewhere beautiful. GODLY!!! Just this part is worth $[amount]. Seriously.
Now, the few flaws. The cookie monster part is just really weird, interrupting the lovely flow of the second movement. There's a few other parts too, that may seem out of place, but if you remember that this is supposed to be a symphony to water, the whole piece does represent the spectrum of changes in water.
This is simply a masterpiece of music. I don't know where you'd be able to categorize it. It needs to be heard, enjoyed, and respected. I've never heard any of Oldfield's other stuff, but this is beyond words. Godly, masterpiece, genious, all can be used to describe this, but you won't get the full idea unless you listen to it with an open mind.
The next time I heard "Tubular Bells" was on a Pure Moods CD. I then purchased the DVD of "The Exorcist" and was thrilled to hear the song in the movie since I wasn't familiar with how it was used in the film. I have to agree with other reviewers, it is a masterpiece. Completely original even to this day. Tubular Bells is a great song to put in your car stereo while you are driving on a cloudy, dreary, rainy day.
The album is a worthwhile purchase if you dig ambience music. Also try to check out a remake of this song by "The Book of Love" although it may be difficult to find.
So,Branson himself founded a new record label,called "Virgin",because of his knowledge about the industry and his newby status on it.The first record they ever put out was "tubular bells".And the rest is history:after that, the main melody appeared on "The exorcist",and its fame just exploded.
Now,in 2003,Mike is a sort of an outsider,selling very few records in comparison to his golden years,besides,being repetitive and predictable to say something.
But this is a must,a lifetime work.A piece of timeless inspiration encapsuled in a CD.At this very moment,he should be retired,but deserving every honor and praise.
What's Tubular Bells? Well,that's the million dollar question.The best thing you can do is to listen to it carefully and try to describe it for yourself.It's a personal experience.
For me,it's a sound collage of sensations and mental landscapes that Olfield put into a record, using a full tapestry of instruments.
He did well mixing both classical and rock ways, to be precise, in an UNIQUE way.No one have made it before or after.
There are really weird,strange,allucinogen pieces of music in here, extracted from a damaged or distraught mind.Delicious melodies delicate as glass shattered by beats that turn them into smithereens; guitar lightning shining in the blackest twilight.Read more ›
Like two other full album songs that I like, Jethro Tull's "Thick As A Brick" and "A Passion Play", I like how the music was written, and how it was based on a classical style of writing than the normal way during the early 70s'.
The music has constrasting sounds, while an organ is playing a dreamy wave, a guitar is sounding very rigid. The two are put together well because their is no cover up to this.
On my last note, I find this album to be more relaxing than freaky and other emotions like that. So try out this album, because everyone deserves to hear a song over 20 minutes once in their life. If you like part two, that is great, but I think the way it is described in how it was written, the first part seems to be the more enjoyable and inspired piece on this album.
Most recent customer reviews
Terrific to hear the whole album again - I wore out 2 vinyl versions in my youth - the CD sounds great - but I was disappointed at the big moment - that point where our conductor... Read morePublished 8 months ago by Amazon Customer
Why do some (including the original artist) feel the need to "improve" upon their own classic works? This remix is a product of a different, mature, Mike Oldfield. Read morePublished 12 months ago by Lawrence Glazer
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- Music > Pop
- Music > Rock > Progressive > Electronic
- Music > Rock > Progressive > Progressive Rock
- Music > World Music > Europe > British Isles


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I just finished re-reading 'The Three Musketeers' - a genuine page turner!
("I was glued to every page!!!")
("slams the reader like a torpedo!")
It's interesting how the great sins of murder and adultery went hand-in-hand in the Europe of those days, both equally deserving of the death penalty,at least when the latter was committed by a woman. When a man committed adultery, it was known as 'having a good time'.
Of course "Western Civilization" has nothing in common with "Radical Islam" (besides the subjugation of women, of course, oh, and fanatical nationalistic evangelism, and the all-powerful macho monotheism, and the sacred places of worship thing ... and so on)
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By Tom Lichtenberg – April 26, 2007Anyone around my age should remember the " 15-year-old Perfect Master ". He was some kid from India whose mom was a hell of a promoter. They sold out stadiums across the nation in the early 1970's, and had some famous followers like Jerry Rubin, if I'm not mistaken. Still, I wonder what happened to that guy. Since he was about the same age as me, he'd be a forty-something perfect master by now. At the time I was confused about that. I thought he was the 'Perfect 15-year-old Master', as if they had a Perfect Master for every age, and they'd all get bumped up every year, like Father Time. I wondered how they managed to co-ordinate all their birthdays, or whether to be a Perfect Master you even had to be born on a certain day, in order to facilitate that transition. The great thing about being a Perfect Master is it seemed you really didn't need any special skills, except perhaps plumpness and sitting still . I didn't have either of those traits a
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Venous Access Devices (cont.)
When to Seek Medical Care for a Venous Access Device
Patient Comments
Call or visit a health care provider right away if a central venous access device is inserted and any of the following symptoms occur:
Go directly to the nearest hospital emergency department in any of the following circumstances:
In particular, shortness of breath, chest pain, or sudden changes in mental status may indicate a dire emergency, and the person with the venous access device should go to an emergency department immediately.
Exams and Tests for Venous Access Device Complications
If a central venous access device is present, the health care provider, whether a primary care provider, specialist, or emergency provider, will have a heightened awareness of the problems that can occur. The provider will ask about symptoms and perform a physical examination.
Some of the following tests may be performed:
Venous Access Device Follow-up
The venous access device can be removed when it is no longer needed, such as when the medical problem for which it was inserted has resolved.
Proper home care of a venous access device involves regular irrigation with a drug called heparin to prevent clotting (except with Groshong-type catheters) and attention to a sterile technique to keep the device free of infection.
Follow any instructions given by the health care provider or nurse to care for a venous access device at home.
Medically Reviewed by a Doctor on 5/18/2016
Medical Author:
Mark Horattas, MD
Kathryn L Hale, MS, PA-C
Medical Editor:
Alan D Forker, MD
Medical Editor:
Francisco Talavera, PharmD, PhD
Medical Editor:
Jonathan Adler, MD
(Page 4 of 6)
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John J. Schomaker, 69, of Wamego, died Monday, Feb. 16, 2015, at Stormont-Vail Hospital in Topeka. John was born on Sept. 27, 1945, the son of Bernard and Minnie (Wells) Schomaker in Humboldt. He is survived by his wife, Betty; three daughters: Micki Schomaker, Kristi (Christopher) DeLeon and Wendy (Kevin)
Melody A. "Judy" Boltz, 65, of Alma, died Sunday, Feb. 15, 2015, at her home. Her family provided the following information. Melody was born Jan. 21, 1950, in Council Grove, the daughter of Raymond and Sherry (Matthews) Andres. She graduated from Manhattan High School with the class of 1968. Melody's
Berneice Faye Robertson, 73, of Wamego, died Wednesday, Feb. 18, 2015, in Wamego. She was born Jan. 21, 1942, in Freedom, Oklahoma, the daughter of Ernest and Vona Feland Stewart. Berneice was a homemaker and day care provider in her home for 26 years. She was known for her cooking
Nell Ann Adams, 87, of Enterprise, died Monday, Feb. 16, 2015, at Enterprise Estate Nursing Center. She was born Dec. 18, 1927, in Pearl and was the daughter of Henry and Leola (Taylor) Rutz. Nell Ann graduated from Chapman High School in 1945. She married Edmond Adams on July 27, 1946, and together
Susan Olive Urban, 76, died Monday, Feb. 16, 2015. She was born on July 28, 1938, in Wapello County, Iowa, to Samuel and Olive (Davis) George. Susan graduated from Manhattan High School in 1956. Susan worked at Glendale Samaritan and Banner Thunderbird hospitals and retired after 26 years of service. Susan will
Harold G. Johnson, 90, of Rapid City, South Dakota, and formerly of Wamego, died Saturday, Feb. 14, 2015, at Rapid City Regional Hospital. Harold was born July 20, 1924, in Manhattan to LeRoy and Myrtle (Gittings) Johnson. He graduated from high school at Wamego and served in the U.S.
Mabel Agnes Bailey, 92, of Belvue, died Tuesday, Feb. 17, 2015, in Manhattan. She was born July 10, 1922, in rural Auburn, the daughter of George A. and Bertha Cellars Moore. Mabel worked as a cook in the food service department at Kansas State University. Her faith was very important
Joe Ellis, 82, of Leonardville and formerly of Manhattan, died Tuesday, Feb. 17, 2015, at Leonardville Nursing Home. His family provided some of the following information. Joe was born on June 22, 1932, in Seligman, Mo., to Jeff and Mary Ellen Ellis. On May 7, 1950, he married his high school sweetheart,
M. Dean Goff, 87, of Manhattan, died Tuesday, Feb. 17, 2015, at the Good Shepherd Hospice House, from complications of cancer. His family provided some of the following information. Dean was born on Sept. 6, 1927, in Manhattan, the first son of Marvin Albert and Edith Elsie (Russell) Goff. The
Alma Ruth Rowlands 96, died Sunday, Feb. 8, 2015, at Meadowlark Hills in Manhattan. Her family provided some of the following information. She was born Alma Ruth Crippen, Feb. 28, 1917, to Clarance and Annie (Mitchell) Crippen in Rago. A foster child at 18 months, Alma had an innate, unwavering faith
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July 29, 2016
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Use Pill Finder Find it Now See Interactions
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18. Picture of Nevus of Ota Treatment
Image Source: Color Atlas of Cosmetic Dermatology Marc R. Avram, Sandy Tsao, Zeina Tannous, Mathew M. Avram Copyright 2011 by The McGraw-Hill Companies, Inc. All rights reserved.
Nevus of Ota, also known as nevus fuscoceruleus opthalmomaxillaris, represents a benign partially confluent macular brown-blue pigmentation of the skin and mucous membranes in the distribution of the first and second branches of the trigeminal nerve. It may be unilateral or bilateral. The ipsilateral sclera is frequently involved.
The photo above shows significant clearance after serial treatments with Q-switched ruby laser on Nevus of Ota.
Text Source: Color Atlas of Cosmetic Dermatology Marc R. Avram, Sandy Tsao, Zeina Tannous, Mathew M. Avram Copyright 2011 by The McGraw-Hill Companies, Inc. All rights reserved.
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I have a set of checkboxes which when checked they pass the value as 1, otherwise they pass the value as 0. However, instead of sending the value of the unchecked checkboxes as '0', the value being sent is 'NULL'.
I have the following JS code in place that should set the value to 0/1 accordingly, however still the value is sent as NULL. Is there anything that can be done to make sure that the value passed in case of an unchecked checkbox is 0?
$('#cb1, #cb2, #cb3, #cb4').on('click', function ()
$(this).val(this.checked ? 1 : 0);
UPDATED Here is my html:
<input type="checkbox" name="cb1" id="cb1" value="1" checked />
<input type="checkbox" name="cb2" id="cb2" value="1" checked />
<input type="checkbox" name="cb3" id="cb3" value="1" checked />
<input type="checkbox" name="cb4" id="cb4" value="1" checked />
They are all checked by default.
If one of them is unchecked, MySQL is reporting the following error: 0SQLSTATE[23000]: Integrity constraint violation: 1048 Column 'ColumnName' cannot be null.
This is because the columns are set to set not to be Null. And even though I have set the default value to 0, once I click on the submit button I still get the error. I tried to remove the Not NULL property however rather than prefilling the value as 0, the input was NULL in the database.


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Meet, Learn, Experience and Succeed with your peers: more than 1,300 of Manitoba's Executives find the connections, ideas and motivation they need at the Manitoba Executive Group to GROW their businesses and careers.
The Manitoba Executive Group has achieved something many business organizations aim to do, but seldom deliver on.
In today's business landscape, despite best intentions, 'Networking' has become synonymous with 'Selling' and 'Being Sold To'. As a result, one arrives at a typical networking event to find a room full of business card passing, elevator pitches and the inevitable uncomfortable conversation when you discover a competitor. Because networking is looked at simply as a means of driving new business, your average networking event attracts more fisherman than fish, and as a result, almost everyone starves.
The Manitoba Executive Group is not a 'leads club'. Sure, our members find new business through the valuable connections they make with our 1,300+ members, but our events and unique programming are about so much more. We expand your Network to introduce you to meaningful connections with local Executives, helping you grow your business and career and reach your professional potential. Our events in themselves are a draw, boasting unique venues and once-in-a-lifetime experiences, ranging from Movie Premiers, to Race Track days, to Behind-the-Scenes tours, and vital Leadership Workshops.
What the Manitoba Executive Group has achieved, then, is creating an environment where Executives - business owners, CEOs, Vice-Presidents, Executive Directors, Branch Managers and a wide variety of other decision makers - meet with the intention of sharing ideas and expertise, leads and laughs. Or think of us as the "It's-Not-About-Sales" Group. Think of us as that Group that "Does Fun, Not Serious Events". But most importantly, think of us as Manitoba's Premier Executive Networking Organization.
The Manitoba Executive Group - Where Manitoba's Executives Come to GROW.
September 2015 kicks off our most ambitious year to date, featuring over 20 top-notch events. Explore some of our events below, or go to our events calendar


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23 September 2013 at 7:25 AM
Ben Affleck Gets Hugs From Violet After Big Family Outing!
About this photo set: Jennifer Garner leaves her seven-year-old daughter Violet's basketball game after watching her play on Sunday (September 22) in Pacific Palisades, Calif. The… Read More Here
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