Determination of Uncombined Lime in Portland Cement The Ethylene Glycol Method D. R. MAcPHERSON AND L. R. FORBRICH Portland Cement Association, Chicago, Ill.
T
HE determination of uncombined lime, calcium oxide, in Portland cement has been the subject of much study during the past two decades. At present, the glycerol-alcohol method (8)is generally used, but, because of the long time required to conduct a single determination, attention during the last few years has been given to the development of more rapid methods. Among the newer methods is the ethylene glycol method ($?,4),which has been studied in this laboratory in connection with pozzolana investigations. The most important finding of these studies, described below, is that for determining uncombined calcium oxide in Portland cement a modification of the ethylene glycol method of Schlfipfer and Bukowski (Q), requiring about 40 minutes, can be substituted for the glycerol-alcohol method which requires from 1 to 7 hours for completion. The ethylene glycol method is based on the ability of calcium oxide and calcium hydroxide to react with ethylene glycol to form a soluble calcium glycolate which is titratable with standard hydrochloric acid. The reactions involved may be considered to be as follows: CaO
+
or CZHEQ~ + CaCzHaOz Calcium glycolate Ca(OH)2 Ethylene glycol CaCZH402 2HC1 -+ C~HEO~ Calcium glycolate Ethylene glycol
+
+
+
TABLEI. EFFECTOF ACIDIC IMPURITIES CaO Present IMQ.
67 0 54 9 30 6 19.7 6 5
CaO Found
%
Mg.
56 45 23 13 3
3 0 4 4 8
84 82 77 68 58
CaO Neutralieed by Acidic Impurities in 50 M1. of Ethylene Glyool MU. 10 7 9 9 7 2 6 3 2 7
TABLE11. EFFECTOF PRETREATMENT CaO Presenta IWQ.
M g.
CaO Found
%
..
a
HsO or
53.4 52.9 55.7 54.7 63.4 61.4 In addition t o that added during preneutralization of
99 98
97 the ethylene glyool.
2H20
Accordingly, a small quantity of calcium oxide, about 0.3 gram per liter, was shaken with the ethylene glycol for 1 hour at 65" to 70" C. This neutralized the reagent effectively without seriously impairing its ability to take up calcium oxide, since it is capable of dissolving a total of about 2.0 grams per liter under the test conditions described. With the ethylene glycol so treated, the test method became one of measuring the increase in titratable calcium oxide, rather than measuring the total titratable calcium oxide. The results obtained under these conditions are shown in Table 11.
CaClz
According to the method described by Schlapfer and Bukowski, a sample of pulverized cement weighing 0.5 gram is placed in a flask with 50 ml. of ethylene glycol and a small amount of quartz sand to prevent the formation of lumps. The flask is closed by means of a rubber stopper and shaken for 30 minutes in a water thermostat at 65" to 70" C. The flask is removed from the thermostat, the solution filtered, preferably by suction, and the residue on the filter washed several times with small amounts of anhydrous denatured alcohol. The filtered solution is then titrated with 0.1 N hydrochloric acid, using as indicator a mixture of 0.10 gram of phenolphthalein and 0.15 gram of anaphtholphthalein dissolved in 100 ml. of anhydrous denatured alcohol.
Application to Clinkers and Dry Cements With the method thus modified, its applicability to Portland cements was studied. In Table 111 are shown the uncombined calcium oxide contents of a number of cements, clinkers, and the major compounds of Portland cement, as determined by the ethylene glycol and the glycerol-alcohol methods. The average difference between the results of the two methods was less than 0.2 per cent and the maximum difference not greater than 0.4 per cent. Furthermore, the results by the ethylene glycol method were fully as reproducible as those by the glycerol-alcohol method. It appears, therefore, that the modified ethylene glycol method is satisfact,ory when applied to clinkers and dry cements. The chemical data for the cements and clinkers are given in Table IV. It is of interest that for clinkers and cements containing less than about 1.5 per cent of uncombined calcium oxide, the ethylene glycol method generally gave higher values than the glycerol-alcohol method; and for samples containing more than 1.5 per cent calcium oxide, the converse was true. The results of studies by Bessey (1) show the same tendency. The lack of agreement might be due to faults in either or both methods.
Schlapfer and Bukowski stated that it is essential that the ethylene glycol be chemically pure and neutral to the above indicators. However, none of the ethylene glycol obtained by the authors was neutral, and when neutralized by addition of calcium oxide it failed to remain so, reversion being slow at room temperature; but, under the conditions of the test procedure, shaking at 65" to 70" C.,this reversion was essentially eliminated. That acid impurities were present, or developed during the shaking period, was shown by an experiment in which samples of calcium oxide were treated according to the method described above. The results are shown in Table I. Since all the calcium oxide was consunled, it was evident that in every case a part of it had been neutralized during the shaking period, presumably by acidic impurities, thus giving low values for titratable calcium oxide. Manifestly, with the reagent acting in this manner the method could not be used. However, it appeared that if this were merely a matter of neutralizing impurities, a suitable pretreatment of the ethylene glycol should eliminate the trouble. 451
INDUSTRIAL AND ENGINEERING CHEMISTRY
452
high results for cements cured only 3 days. Moreover, both tricalcium aluminate and the calcium sulfoaluminate which was formed in the mixture of tricalcium aluminate and gypsum (5th line) appeared to be decomposed, especially the latter. This confirms results obtained by Schlapfer and Esenwein ( 5 ) . The low results obtained with cements cured 2.5 to 3.5 years are believed to be the result of incomplete solution of the calcium hydroxide which, during the long curing period, formed crystals of such size that they were not readily soluble. This has been partly confirmed by determining the solubility of crystalline calcium hydroxide in glycerol-alcohol following the procedure of the glycerol-alcohol method, and in ethylene glycol. The calcium hydroxide was dissolved almost quantitatively by the glycerol-alcohol, but only 68 per cent was dissolved by the ethylene glycol. _.
TABLE111. COMPARISON OF TFLE GLYCEROL-ALCOHOL AND ETHYLENE GLYCOL METHODS
Material
Reference Number
Uncombined Calcium Oxidea GlycerolEthylene alcohol glycol method methodb
% Clinker Cement
1
2 31 2 3 4 65
7
8
Tricalcium silicate Dicalcium silioate Tricalcium aluminate Tetracalcium aluminoferrite CaS042HzO
0 0 0.3 0.4 0.5 0.5 0.7 0.0 0.7 0.8 1.0 1.1 1.0 1.2 1.5 1.8 1.9 2.0
9 10 11 12 13 14 15 16 17 18 19 20 21
2.3 2.4 23 . 8 3
2.0
1
0.7
2
0
3
0
4 5
0
0
Deviation from QlycerolAlcohol Method
%
%
0 0 0.1 $0.1 0 . 41 $ +00..11 0.4 0 0.8 $0.3 0.9 +0.4 0.9 0.8 $0.2 +0.2 0.7 0 1.0 $0.2 1.0 0 1 . 03 $0.3 -0.1 1.3 $0.1 1.6 $0.1 1.6 -0.2 1.9 0 1.6 -0.4 1.8 -0 2 1.9 -0.4 2.3 -0.1 2.5 -0.3 3.2 -0.1 Av. difference 0.16 0.7 0
TABLEV. RESULTS WITH HYDRATED CEMENTS
Hydrated Material"
0
0 0.1
$0.1
Trace 0
0 0
CSS
czs
CaA CiAF 81'7 CsA
-
Eaoh value ia the average of two determinations in good agreement. b Modified as desoribed in the text.
Q
Application to Hydrated Cements I n the study of the ethylene glycol method applied to hy-
No.
1 2 3 4
..
Deviation from Length of GlycerolCuring Aloohol Period a t Method 70-75' F. % Years
%
%
30.1 0.3 0 0
6 3 0.4 0.7 0.3
+$ 00..17 $ 0.3
2.5 2.5 2 5 2.5
0
5.2
$ 5.2
2.5
68.4 12.2 9.1
-30.7 -11.5 -11.9
25.1
+ 1.4
,---\
-23.8
l;a(uti)z (crystalline) Cement Cement
36 37
99.1 23.7 21.0
Cement
38
23.7
38
17.8
18.9
$ 1.1
3
38
15.2
17.3
+ 2.1
3
+
6
3'.k 3.5
Dave 3
a All hydrated materials dried a t 150' C. for 2 hours in carbon dioxidefree air except the hydrated mixture of CaA and CaS04.2HzO which was airdried a t room temperature. b Each value is the average of two determinations in good agreement.
12 15 6
6 6 12
3.05 0 2.54 0 3.10 0
Lab. preparedb
5
10 5
5.24 1.22 1.98 0.98 0.68 3.21 2.26 1.15 1.11 19.03 4.58 1.20 1.11 1.45 2.70 1.34
Commercial Commercial S ecial cement &mmercial Commercial Commercial Commercial Commercial Commercial Natural cement Commercial Commercial Commercial Commercial Commercial commercial Commercial Commercial Commercial Commercial Commercial
11 ,
. ..
13
11
11 16 12 10 10
5 8 10 6 10
'9
7 14 10 9 9 13 10 6
10 12 12 11 8 11 12 10 10 14
..
8
11 9
1.49
3.76 4.12 0.98 1.26
3.1 2.6
...
3.2 23 .. 61 3.2 2.9 3.1
...
2.8 2.7 3.1 2.7 3.2 3.8 3.3 3.2 2.9 2.7 2.8
Commercial Lab. preparedb
Abbreviations used: tricalcium silioate, Cas; dicalcium silicate, C B ; tricalcium aluminate, CxA; tetracalcium aluminoferrite, CaAF. b The laboratory-prepared clinkers were obtained from the Portland Cement Association Fellowship , at the National Bureau of Standards, Washington, D. c. Q
Uncombined Ca(0H)zb Glycerol- Ethylene Ref. alcohol glycol No. method method
The high results for cements cured 3 days may be accounted for by assuming that the calcium hydroxide when first formed is amorphous, or very finely crystalline, and hence readily soluble; and then by assuming further that the additional calcium hydroxide came from the decomposition of DATAON CLINKERS AND CEMENTS USED TABLE IV. CHEMICAL t h e h y d r a t e d a l u m i n a compounds. --Chemical AnalysesPotential Compound Composition5 T h i s p a r t l y confirms the findings of Si09 FeJOa All08 CaO SO1 Loss CsS CIS CsA CiAF MgO Cas04 Remarks Bessey ( I ) . % % % % % % % % % % % %
Clinkers 23 76 2 07 6 08 64 28 0.07 0 17 45 34 22'03 2 ' 0 2 7'01 65'49 0.18 0128 49 26 23:50 3192 5:30 63:39 0.09 0.18 45 34 Cements 1 22 56 3 14 4.03 61 82 1.82 0 77 42 33 2 23'26 1'53 6 19 65:67 1.54 1'37 48 31 3 22'76 4'40 3 ' 6 1 63 68 1 2 6 1:44 . 4 20'71 3'59 7100 64:95 1:87 0.71 52 20 6 22:72 1170 5.36 66.52 1.61 1.13 53 26 6 20 36 2 48 7 44 62 71 1 84 1 . 0 4 39 29 7 21'48 3'20 6'61 62'85 1'87 1.05 35 35 8 22:92 1:85 5:05 63164 1:72 3.00 40 30 9 20.50 3.35 5 . 0 7 64.49 1.84 2.13 53 19 10 23.72 2 78 5.35 44 43 1.66 1.95 . 11 20.84 2:13 4.75 63:06 1.67 2.25 54 ii 12 20 10 4 46 6 48 64.55 1.60 0 81 50 20 13 20:46 8:30 6:68 64.37 1.80 1:69 46 25 14 20.17 3 10 6.66 63.90 1 61 2 35 46 24 15 19.94 2:90 6.06 64.09 1:89 1:70 59 19 16 21 34 4 13 5.51 63.27 2.26 1 47 38 33 17 21:24 3:28 6.18 64.27 1.92 1:27 39 32 18 20.30 2.10 5 72 63 47 1 . 8 5 2.44 48 22 19 20.22 2.58 5:24 63:84 1.72 1 . 1 5 52 13 20 20.00 3 . 7 3 6.05 64.84 1.57 1.92 50 20 21 18.58 2.93 7.07 66.23 1.67 1.68 54 13 1 2 3
f 19% 8aSOa.ZHzO
Cement Si02 aq. f3% Cement 10% Si02 aq.
drated cement, the glycerol-alcohol method was again used as the reference method because it was found by Work and ~~~~~t~~ (6)and by the authors to be satisfactory for set cements. The results obtained for several hydrated cements and the pure compounds are shown in Table V. The ethylene glycol method did not appear to be satisfactory when applied to hydrated cements. It gave low results for cements and tricalcium silicate cured 2.5 to 3.5 years and
Ref.
VOL. 9, NO. 10
General Comments The use of technical ethylene glycol which contains not more than 0.5 per' cent of water was found satisfactory. The cost of the technical grade is approximately one-fifth that of the chemically pure variety. Since ethylene glycol has a tendency to decompose in sunlight, it must be stored in dark-brown bottles and frequent blank determinations should be made on the pretreated ethylene glycol t o determine its alkalinity. A tendency toward lower results was noticed when the shaking period was extended beyond 30 minutes; however, the results, in most cases, were not greatly affected up to about hour, Because carbonation during filtration
OCTOBER 15, 1937
ANALYTICAL EDITION
453
Schlapfer and Bukowski were replaced by the apparatus shown in Figure 1.
Summary and Conclusions The applicability of the ethylene glycol method of Schlapfer and Bukowski t o the determination of uncombined calcium oxide or hydroxide in Portland cements, clinkers, and hydrated cements was studied. When modified, the ethylene glycol method, which requires only 40 minutes for a complete determination, is satisfactory for determining uncombined calcium oxide in clinker and Portland cement, and may be substituted for the glycerolalcohol method which requires from 1 to 7 hours for completion. The ethylene glycol method cannot be recommended for determining uncombined calcium hydroxide in hydrated Portland cement because, in the older samples, it is not completely dissolved, presumably on account of its coarsely crystalline state, and because hydrates of the alumina compounds decompose in the presence of ethylene glycol.
Aclcnowledgment Acknowledgments are due to C. L. Ford and to the Universal Atlas Cement Co. for chemical analyses of the cements and clinkers used in this investigation. FIQURE~
1. AIR THERMOSTAT WITH SHAKER
may cause relatively large errors, it is recommended that the filtering process be carried out as rapidly as possible to minimize this effect. The use of a Gooch crucible with a very thin asbestos mat is satisfactory. The size of sample of calcium oxide used for standardizing the acid should not greatly exceed 60 mg. when 50 ml. of ethylene glycol containing about 0.3 gram of calcium oxide per liter are used. This limitation is necessary to assure quantitative conversion of the calcium oxide into calcium glycolate during the 30-minute shaking period. The mater thermostat and shaking apparatus proposed by
Literature Cited (1) Bessey, G.E.,Cement, 9,163-8 (1936). (2) Bukowski, R.,Tonind.-Ztg., 59, 616 (1935); Rock Products, 38, 50 (1935). and Bogue, R. H., IND.ENQ.CHEM.,Anal. Ed., 2,296-8 (3) Lerch, W., (1930). (4) Schlapfer, P., and Bukowskii, R., Lab. f6dbral essais matdriaux annex6 dcole polytech. f6ddrale Zurich, No. 63 (1933); (Eidgenbss. materialpriifungsanstalt E. T . H . Ziirich, Rpt. No. 63)+ (5) Schlapfer, P., and Esenwein, P., Zement, 25, 814-16 (1936). (6) Work, L.T.,and Lasseter, F. P., Concrete, Cement Mill Ed., 38, NO.3, 81-6, NO,4,89-92,NO.6,79-84 (1931). RECEIVED August 6, 1937.
Intensity and Stability of Ferric Thiocyanate Color Developed in 2-Methoxyethanol H. W. WINSOR, Agricultural Experiment Station, University of Florida, Gainesville, Fla.
0
F THE reagents used in colorimetry, thiocyanate for iron is one of the best, but the method has never been completely satisfactory because of the rapid fading of the color when developed in water solution. Previous to 1900 several workers in Europe found that ether, amyl alcohol, and acetone when used in conjunction with the method, inhibited dissociation of the ferric thiocyanate and helped to preserve the color. The use of acetone for that purpose was introduced in this country by Marriott and Wolf (4) in 1906. Miller, Forbes, and Smythe ( 5 ) reported its successful use in 1929. Fowweather (8) employed an acetone-water mixture in which the vapor pressure was lowered by using 50 per cent water in the final volume; but Wong (10) avoided the use of acetone because of its very rapid evaporation.
As an alternative, the extraction of ferric thiocyanate by a solvent immiscible with water is, a t best, an undesirable technic; and the work of Tarugi (6) indicates that such extraction is not strictly quantitative. Acetone is definitely superior to water as a medium for this determination, yet offers serious disadvantages to practical use. Its rate of evaporation is so great as to be a disturbing factor in precise analysis, and with thiocyanate it slowly forms a flocculent white precipitate which must be filtered out. Moreover, the hypothetical ideal does not obtain, because acetone, a much weaker solvent for inorganic salts, cannot be completely substituted for water. Miller, Forbes, and Smythe used the highest practicable ratio of acetone to water-about 78 per cent of acetone by weight. Yet, because of the high dielectric value of water, the 22 per cent
