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Volume 58, 1928
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Estimation of Carbon by Wet Combustion.

[Read before Philosophicai Institute of Canterbury, 1st September, 1926; received by Editor, 31st December, 1926; issued separately, 15th August, 1927.]

This paper is a short account of work done when in search of a method for the accurate estimation of small quantities of alcohol; it is followed by a short list of references to wet combustion methods.

The wet oxidation methods have been used for a variety of purposes, from the estimation of carbon in steel to the estimation of organic matter in soils and agricultural products. Many modifica-tions of these methods are to be found in the literature, the variations being often developed to prevent the spray or mist which is formed during the reaction from being carried over into the absorbent for the carbon dioxide.

The methods may be divided into two classes; first, those in which the carbon is completely oxidised to carbon dioxide, this being absorbed, after washing and drying, in standard alkali, or in weighed soda-lime or potash tubes; and, second, those in which standard solu-tions of potassium di-chromate, etc., are used, the excess of oxidizing agent being estimated by suitable means.

Class 1.

The apparatus used in the experiments described below was a modification of that used by Hibbard (4) which is in turn modified from that of Truog (10). The oxidation was carried out in a 250 c. C. hard glass round-bottomed flask, the neck of which had been ground to fit a large hard glass condenser, the distance between the neck of the flask and the bottom of the water-jacket being about four inches. Into the top of the condenser was fitted a double-bored rubber stopper, one hold to admit the reagents and pure air, the other to carry the outlet tube to the train of drying tubes, etc. The reagent was admitted drop by drop, first the chromic solution and then the acid, through a tube which reached below the level of the mixture in the reaction vessel, while a slow stream of carbon dioxide-free air was drawn through the apparatus. The gas evolved was purified and dried through a U-tube containing pure granulated zine, two bubblers containing concentrated sulphuric acid, and finally through two U-tubes with fresh calcium chloride. A U-tube containing soda-lime was used to absorb the carbon dioxide; between this tube and the filter-pump a calcium chloride guard tube was placed.

To carry out an exeriment a known volume of liquid containing the carbon compound in dilute solution is placed in the reaction vessel and a slow stream of air drawn through. Then the reagent is slowly admitted, all the time warming the flask with a small flame. The liquid darkens and becomes almost black; small bubbles of carbon dioxide soon begin to rise through the liquid, when the

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heating is moderated until the reaction is nearly finished, after which the liquid is boiled for twenty minutes. An experiment can be com-pleted in an hour.

When concentrated sulphuric acid is used in the oxidizing mixture a thick fog forms and passes into the U-tubes, but passage of the gas through constant boiling point acid is said to remove the mist particles (11). If phosphoric acid (sp. gr. 1.75) is used this fog does not form; moreover the liquid does not darken to the same extent as with sulphuric acid.

The oxidizing solution is made up as follows: 170 g. of pure chromic oxide are dissolved in 300 c. c. of distilled water to which 25 c. c. of concentrated suphuric acid are added, the whole being then boiled to oxidize any organic matter which may be present. When cold the solution is made up to 500 c. c. with water (4).

A quantity of the compound is taken such that 0.10 to 0.15 g. of carbon is present. In general 15 c. c. of the chromic solution and 25 c. c. of sulphuric (or phosphoric) acid are used for oxidation; about 100 c. c. of carbon dioxide-free water are used for dilution in the reaction vessel.

With solid materials this method gave good results, especially with a comparatively easily oxidized substance like oxalic acid. With acoholic solutions, however, the results were hopeless; oxidation proceeded practically only as far as aldehyde, this being absorbed in the sulphuric acid bubblers, while a small quantity of carbon dioxide was formed and absorbed in the soda-lime tube. Even when the vapour leaving the reaction vessel was passed through a hot tube containing palladiumized asbestos, the results were very little better. Oxygen from a cylinder was also used instead of air, but even in this case no useful results could be obtained.

Two standard solutions were made up: (1) saccharose, 1 g. in 200 c. c. of carbon dioxide-free water, and (2) oxalic acid 2 g. in 200 c. c. of water. In table 1 are given some of the data obtained; with oxalic acid phosphoric acid was used in place of sulphuric acid.

Table 1.
Compound Oxidizing solution c. c. Carbon dioxide mg.
Chromic Acid Found Theory
Saccharose 15 25 185.0 191.5
Saccharose 25 25 188.4 191.5
Oxalic Acid 15 25 173.3 173.2
Oxalic Acid 15 25 173.4 173.2

In the analysis of organic compounds containing halogens a slightly different procedure is necessary owing to the evolution of the halogen either free or in combination with chromium; Robertson (5, 6, 7) has worked out the methods for such cases.

Class 2.

Both potassium dichromate and potassium permanganate have been used for the oxidation of alcohol, being of particular use for

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the estimation of small quantities. In the present work neither of the permanganate methods to which reference is made (14, 15) has been tested.

Allen (12) gives a method using a solution of potassium dichro-mate in approximately 40 per cent. sulpuric acid. The standard solution is made up by dissolving 16.97 g. pure potassium dichromate in 200 c. c. of distilled water and then making up to 1000 c. c. with 50 per cent. sulphuric acid. The excess of dichromate after oxida-tion of the alcohol is estimated by titrating with standard (N/10) thio-sulphate the iodine liberated on the addition of potassium iodide to the reaction mixture after dilution with 200 c. c. of water. In this method oxidation proceeds to the acetic acid stage, so that 1 c. c. of the dichromate is equivalent to 0.005305 g. of alcohol.

A large number of experiments have been carried out using a standard alcohol solution of such a strength as is expected to be obtained in the later work. The heating of the solution has been varied from slow to rapid, from heating only to 80° C. or to boiling for varying periods of time, but satisfactory results have not been obtained. Allen merely states that the solution is to be heated until a green but not a greenish-yellow tint is reached, but the difficulty is to decide when the solution has reached the right stage since the experiments described here have shown that alhough visually the solutions are at the same stage, the oxidation has not proceeded to the same degree; indeed, in many cases, oxidation must have gone beyond the acetic acid stage to explain the large consumption of dichromate. The results are very erratic, sometimes low, sometimes high, and sometimes approximately correct, although the tendency is distinctly towards high results.

In all cases the total volume of reaction mixture was about 150 c. C. Heating must be carried out carefully, especially in the early stages, otherwise loss of alcohol occurs.

Table 2 contains some of the results obtained when the various factors governing the oxidation were altered.

Table 2.
Alcohol mg. Error
per cent.
Dichromate
solution c. c.
Heating
Theory Found Temp. °C. Time mins.
108.3 107.2 −1.0 27.0 (Boiled) 10
108.3 117.8 +8.8 25.0 (Boiled) 20
108.3 113.5* +4.8 23.0 80 10
108.3 117.2* +8.2 23.0 85. 10
108.3 109.0 +0.6 23.0 85 10
104.7 101.1 −3.4 21.1 90 2
104.7 105.3 +0.6 22.0 90 5
104.7 110.3 +5.4 22.0 90 15
104.7 106.0 +1.3 23.0 80 15
104.7 109.2 +4.3 23.0 75 20

[Footnote] * In each of these cases 10 c. c. of concentrated sulphuric acid were added to the reaction mixture.

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In the other method (13) using potassium dichromate as oxidizing agent, the whole reaction is carried out in concentrated sulphuric acid. The solution is made up by dissolving 4.4128 g. of pure dichro-mate in as small a volume of water as possible and then making up to 1000 c. c. with concentrated sulphuric acid, being careful to add the acid slowly, so that at no time shall the temperature rise above 100° C. At a certain stage the chromic oxide. precipitates out but readily redissolves when more acid is added. From a burette a measured quantity of the solution is run slowly into a cold mixture of a known volume of acoholic solution with three times its volume of concen-trated sulphuric acid, which has been added slowly, keeping the flask cool under the water tap. The mixture is then slowly heated to 98° C. (not above) and the temperature held there for exactly five minutes. After cooling the liquid is diluted with 200 c. c. of cold water, and after cooling again the excess dichromate's is destroyed by excess of standard ferrous ammonium sulphate solution, this excess in turn being estimated with standard permanganate.

The method sounds long and involved, but in practice it is rapid, and gives accurate and reproducible results. In very few cases did the quantity of alcohol present in the volume of liquid taken exceed 10 mg., and in the great majority of cases it was considerably less than this.

In Table 3 are given the results of experiments made to test the accuracy of the method using alcoholic solutions of known strength. Solution A was made up from industrial absolute alcohol which was taken to be 99.5 per cent. pure, but in reality may have been only 98 per cent, which would explain the low results of the first three experiments as compared with the experiments using solution B for the making of which pure alcohol was used.

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Table 3.
Solution Alcohol mg. Error per cent. c. c. conc. sulph. acid per 10 c. c. of solution.
Theory Found
A 10.56 10.21 −3.0 30
A 12.15 11.95 −1.7 23
A 21.12 20.70 −1.5 25
B 20.00 19.95 −0.25 30
B 20.00 20.06 +0.30 30

It is necessary to point out that this method cannot be used in the presence of chlorides as evolution of chlorine occurs and high results are obtained. Thus a given quantity of solution contained 10.56 mg. of alcohol; after adding 1 c.c. of N/10 sodium chloride and treating as above an apparent result of 12.27 mg. was obtained. Silver sulphate may be used to remove chloride.

An alcoholic soda solution, prepared for use in the main series of experiments, was then analyzed by the above method. Into a weigh-ing bottle were rapidly placed 10.2940 g. of this solution which were

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afterwards diluted to 1,000 c. c. with distilled water. Of this dilute solution 15 c. c. were taken for analysis. Six experiments were made using two different lots of dichromate solution. The mean values for the alcohol content from the two sets were 7.75 per cent. and 7.60 per cent. respectively; in no case did the extremes in each set differ by more than 0.1 per cent.

A large number of analyses have been carried out using this method when even as little as 0.05 g. of approximately 10 per cent. alcoholic solution (which had to be diluted down to 100 c. c. before estimation) was available, and it can be confidently stated that accurate results are obtained when reasonable care is observed.

The list of references refers more particularly to methods in which the evolved carbon dioxide is estimated. In the second class the methods are for ethyl alcohol only.

Summary.

1. Carbon may be estimated by wet combustion with dichromate in acid solution when present in non-volatile compounds.

2. Ethyl alcohol may be estimated by volumetric methods even in very dilute solution; attention is drawn particularly to Benedict and Norris' modification of the method which can be used when only 0.01 per cent. of alcohol is present.

The above experiments were carried out at the Imperial College of Science and Technology, South Kensington, London.

List of References.
Class
1

1. Ames, J. W. and Gaither, E. W. Journ. Ind. Eng. Chem., vol. 6, 1914. p. 561.

2. Cain, J. R. Journ. Ind. Eng. Chem., vol. 6, 1914, p. 465.

3. Gortner, R. A., Soil Science, vol. 2, 1916, p. 395.

4. Hibbard, P. L. Journ. Ind. Eng. Chem., vol. 11, 1919, p. 941.

5. Robertson, P. W. Journ. Chem. Soc., vol. 107, 1915, p. 202.

6. Robertson, P. W. Idem., vol. 109, 1916, p. 215.

7. Robertson, P. W. Chem. News., vol. 120, 1920, p. 54.

8. Schollenberger, C. J. Journ. Ind. Eng. Chem., vol. 4, 1912, p. 436.

9. Schollenberger, C. J. Idem., vol. 8, 1916, p. 1126.

10. Truog, E. Idem., vol. 7, 1915, p. 1045.

11. White, J. W. and Holben, F. J. Idem, vol. 17, 1925, p. 83.
Class 2.

12. Allen. Organic Analysis, vol. 1, p. 349.

13. Bendict, F. G. and Norris, R. S. Journ. Am. Chem. Soc., vol. 20, 1898, p. 293.

14. Allen. Loc. cit.

15. Astruc, A. and Radet. Journ. Soc. Chem. Ind., vol. 441, 1925, p. 373B.