(-1)
Diehl, H., Goetz, C. A., Hach, C. C., J . Ani. Water Works Assoc. 42, 40
(1950). ( 5 ) Harvey, .4. E., Jr., Komarmy, J. M., Wyatt, G. AXAL.CHEM. 25, 498 (1953). (6) Knight, A . G., Chenzistrg & I n d u s t r y 1951, 1141.
(7) Patton, J., Reeder, W,, ANAL.CHEM, 28, 1026 (1956).
(8) Reilley, C. N., Porterfield, W. W., Zbid.,28, 443 (1956). (9) Schenkel, H., Esperientia 4 , 383 (1948). (10) Schwarzenbach, G., Biedermann, W., Helv. Chim. Acta 31, 678 (1948).
(11) Young, A,, Sweet, T. R., ANAL CHEM.27, 418 (1955).
RECEITEDfor review August 29, 1956. .4ccepted Xovember 21, 1956.
N e w Complexon for Titration of Calcium in the Presence of Magnesium R. W. SCHMID and CHARLES N. REILLEY Department of Chemisfry, University of North Carolina, Chapel Hill, N. C.
b The complexometric determination of both calcium and magnesium has always involved a precipitation step for one of these metal ions. This step i s eliminated b y titration with the complexon, ethylene glycol bis(P-aminoethyl ether)-N,N'-tetraacetic acid, which complexes calcium (log K = 10.7) selectively in the presence of magnesium (log K = 5.4). The sum of calcium and magnesium i s determined b y titration with (ethylenedinitril0)tetraacetic acid, and magnesium by difference. A mercury indicator electrode i s used for detecting the end points potentiometrically. Log K values of 23.8, 10.7, 8.1, 8.0, and 5.4 (ionic strength = 0.1, 25" C.] were determined for the mercury(ll), calcium, strontium, barium, and magnesium complexes of ethylene glycol his-(@aminoethyl ether)-N,N' -tetraacetate.
Hh complexometric deterinin a t'ion T o f ca 1ciuniand magnesium has found
wide application in the analysis of vater, limestones, soils, and physiological materials and the numerous publications on this subject have been ieviewed (7, 12, 15). Several methods have been suggested for the determination of calcium and magnesium with (ethylenedinitri1o)tetraacetic acid (EDTA or H4Y)in a mixture of both. The most common proccduic (>onsists in the titration first of the sun1 of calcium and magnesium with (ethylenedinitri1o)tetraacetic acid in an ammonia buffer using Eriochrome Black T as indicator. Kext. the magnesiuni in a second poition of the sample is precipitated as the hydroxide at a pH of approximately 13, and the calcium alone is then titrated lvith (ethylenedinitri1o)tetraacetic acid using murexide as indicator (5, 11, 16). The niagnesiurn hydroxide, however, always 1 etains some of the calcium, with the iesult 264
ANALYTICAL CHEMISTRY
that low values for calcium are obtained. This source of error apparently can be eliminated by a back-titration procedure (3, 8). Other workers advocate the separation of calcium from the mixture as the oxalate (1, 2, 6), sulfite (9), or sulfate from a methanol solution (10). Separation by ion exchange chroniatography prior to titration has also been applied (4). I n the present article a procedure is proposed which avoids a chemical separation of the two elements by employing a titrant which will selectively complex calcium. DEVELOPMENT
Mercury as a pM Indicator ElecI n previous work ( I S ) a trode.
mercury electrode was found t o be useful for the end point detection in coulometric titrations of copper(II), zinc(II), calcium(II), or lead(I1) with electrolytically released (ethvlenedinitrilo) tetraacetate. T h e application of t h e mercury electrode as a p M indicator electrode for metal ions other than mercury requires the piesence of a chelating agent which forins a complex with both mercuric ions and the other metal ions concerned. For the electrode system HgIHgZ--, lleZ--, Me++ the following relationship is T-alid a t 25O
c:
Ke.2 and KWL are the stability constants of the mercury and metal chelate complex respectively; v indicates the charge on the metal ion; and Z-"is the anion of the completely ionized chelating agent. At constant concentrations of mercury chelate complex
and metal chelate complex, the potential of the mercury electrode according to Equation 1 depends linearly on the pM. This is the fundamental basis for the application of the mercury electrode in complexometric titrimetry. I n a complexometric titration nith potentiometric end point detection a small amount of mercuric chelate complex is added to the solution of the metal ion to be titrated in order to provide the components necessary for the indicator electrode. During the course of the titration the potential of the mercury electrode then varies in a similar way with the amount of added titrant as the potential of a glass electrode varies in a pH titration. The properties of the potentiometric end point under various conditions can be elucidated from a potential-pH diagram. Figure l illustrates such a diagram obtained in connection with the determination of stability constants of metal chelates with (ethylenedinitrilo) tetraacetic acid (14). The points of the metal curves are the experimentally evaluated potentials of a mercury electrode as a function of pH for solutions containing (ethylenedinitri1o)tetraacetatoinercurate(I1) complex, a bivalent metal ion, and its (ethylenedinitri1o)tetraacetato complex, each in a concentration of 0.001M and also 0.1M sodium perchlorate to maintain a fairly definite ionic strength. The potentials in the pH independent region vary linearly with the log K of the metal
chelates and may be used to calculate the value of log K ( 1 4 ) . On the other hand, in a complexometric titration, these potentials are the ones which the mercury indicator electrode shows a t the point of half titration using 0.001.U (ethylenedinitri1o)tetraacetomercurate
400
\
X
I’
14 w
-1
a I 12
8
-1
a
10
E
vestigation of the particular conditions in such cases, or the use of other nonreacting buffer systems, is advisable. X,A”,A;”-nitrilotriethanol and acetate, for example, do not form analogous complexes. Selection of Complexon. I n searching after a chelating agent having sufficient difference in the stability constants of its calcium and magnesium complexes t o allow a selective titration of one of these ions, ethylene glycol bis-( paminoethyl ether)-N,Y’tetraacetic acid (EGTA or H4Z) was considered. HOOC-CHZ
\
N-CH2-CH2-0--
Y
HOOC-CH~/
CL
6
/CH&OOH
1
CH~-CH~-O-CH~-CH~-N \CH,COOH
01 2
1
1
I
I
4
6
I
I
I
8
IO
PH Figure 1. Potential-pH diagram for (ethylenedinitril0)tetraacetic acid (Y) system
,
Solution contains 0.001M M e Y - - , 0.001M Me’+, 0.001M HgY--, and 0.1 M NaClO, where Y corresponds to (ethylenedinitrilo)tetraacetic acid. Curves I and II limit the electrode potential in certain p H ranges according to
IHgY-(0.001 M )
II-
HgO
+ n H + + 2e % Hg’ +(0.001 H,Yn-l M) f H,O
+ 2e
(11) complex, somewhat analogous to the p K of an acid in a p H titration. I n practice, a much smaller amouiit of (ethyl’enedinitriloJtetraacetomercurate(I1) complex should be added to the solution to be titrated, for otherwise a sharp end point is not obtained. Although this shifts the absolute value of the potentials ill the diagram, the relative potentials remain the same. Curve I1 in Figure 1 represents the upper limit of the potential of the mercury electrode caused by t,he forniation of mrrcury(I1) oside. Curve I corresponds to the buffer region after the end point in the complexometric titration as denot’ed by the follon-ing electrode reaction: Hg
T
+
HnlTn-4e H g Y Z n H +
+ 2e
(2)
Fmm Figure 1 a choice of the pH witable for a titiation can be made. For instance. zinc at a pH of 6 can be titrated and an end point break in the order of 150 mv. is espected. Calcium a t the sanu, pH would not yield a suitable titi ation curve, analogous to the titration of certain phenols with base in aqueous solution. A t a pH of 8, however, an end point break of 150 mv. will occur also for calcium. Consequently, for a solution containing both calcium and zinc. the zinc can be
Hg’ f 2 0 H -
titrated selectively a t a pH of 5 , whereas a t a pH of 8, the sum of zinc and calcium will be titrated. The amount of calcium can then be calculated by difference. On the assumption that a t least 100 mv. potential difference between two pa1 buffer regions aIe necessary to give a usable end point break, calcium is expected to give a reasonable break above pH 7 . I n the presence of an equal amount of magnesium, no break will occur after the completion of the titration of the calcium because the potential difference between the calcium and magnesium buffer regions is only 53 mv., corresponding to the difference of 1.8 log K units in the stability of the (ethylenedinitri1o)tetraacetato complexes. X useful end point break will occur, however, after the titration of the sum of calcium and magnesium. A buffer is necessary to keep the titration proceeding a t the desired pH. Several commonly used buff e: s, however, form a complex with (ethylenedinitrilo)tetraacetatomercurate(II) (IS) -e.g., ammonia forms HgYNHa--; ethylenediamine forms HgYr\“&H,CH2NHsand HgYNH2CH2CH2XH2--). Therefore other potentialpH relations are encountered with use of such buffers. The potential-pH relation in ammonia buffer is given by Reilley and Porterfield ( I S ) . ,4n in-
Schwarzenbach (15) reports a difference of 5.8 in the log K of calcium and magnesium with this compound (log Kca = 11.0, log K V , = 5.2). He points out that the complexing agents containing ether linkages have a strong tendency to complex the alkaline earths heavier than magnesium. Because of this fact Sch\varzenbach saw a disadvantage in the use of ethylene glycol bis-(Paminoethyl ether)-N,h”-tetraacetic acid for the titration of alkaline earths as the end point in such titrations, based upon the disappearance of the magnesium-Eriochrome Black T complex, would be exceedingly poor. The use of the mercury electrode, however, places the whole problem in a new perspective and the ability to titrate calcium in the presence of magneeium becomes feasible and useful. I n order t o obtain further information about the ethylene glycol bis-@-aminoethyl ether)-h-,X’-tetraacetic acid system. a potential-pH diagram was constructed from experimental data and is illustrated in Figure 2. The stability constants of its various metal chelates may be calculated from the data and these values are listed in Table I. The procedure for the determination of stability constants of metal-complexons by use of the mercury electrode has been described (14) and the same procedure was followed. Values for the acid dissociation constants necessary for these calculations were taken from Schwarzenbach (15). Curve I of Figure 2 for the system, ethylene glycol bis-(0-aminoethyl ether)N,N’-tetraacetatomercurate(I1) and ethylene glycol bis-(p-aminoethyl ether) N,X’-tetraacetic acid (each 0.001M), obtained in 0.1M sodium perchlorate is, within the experimental error, identical with the curve obtained in 0.LV ammonia or in 0.1M K,K’,N”-nitrilotriethanol. The same is true for curves VOL. 29, NO. 2, FEBRUARY 1957
265
Table 1. Logarithms of Stability Constants of Some Metal Ions with Ethylene Glycol Bis-(P-aminoethyl Ether)-N,N’tetraacetic Acid (25” C. and ionic strength of 0.1)
Value Reported hv - d
Metal Ion
Values from Figure 2
Sch-mrzenbach
I11 to VI. This signifies that, contrary to (ethylenedinitri1o)tetraacetatomercurate(I1) (IS), ethylene glycol bis-(flaminoethyl ether)-N, N‘-tetraacetatomercurate (11)does not form a complex with ammonia, a fact which is favorable. Curve 11, however, is shifted 80 mv. more negative in 0.1M ammonia because the positive potential limit is no longer due to the formation of mercury(11) oxide, but to the formation of diammine mercurate(I1) complex. According to Figure 2, within the pH region between 7.5 to 9, a potential break of approximately 140 to 160 mv. is expected for the titration of calcium in the presence of an equal amount of magnesium. Even with a 20-fold excess of magnesium present, the potential break would still be around 100 niv. and therefore the selective determination of calcium is still feasible. Vnfortunately the potential difference between curves VI and I of Figure 2 is too small and a useful second break indicating the completion of the titration of magnesium does not occur. Thus, for the determination of both calcium and magnesium, a separate titration with (ethylenedinitri1o)tetraacetic acid is necessary. To illustrate the analytical applicability of ethylene glycol bis-@-aminoethyl ether)-N,N’-tetraacetic acid and (ethylenedinitri1o)tetraacetic acid in the analysis of calcium-magnesium mixtures, a series of titrations was carried out with the first acid, employing solutions containing various amounts of calcium and magnesium. This allows estimation of the calcium content. Xext, the sum of calcium and magnesium was determined by titration with (ethylenedinitri1o)tetraacetic acid, and the amount of magnesium was found from the difference. EXPERIMENTAL
Ethylene glycol bis( p-aminoethyl ether)-N,N’-tetraacetic acid was obtained from J. R. Geigp A.-G., Basel, Switzerland, in a 98.9y0 assay. A sample, twice recrystallized by dissolution in sodium hydroxide and Reagents.
266
ANALYTICAL CHEMISTRY
dinitrilo)tetraacetatomercurate(II) had to be freshly prepared, because a precipitate usually formed in such solutions after standing several days. Apparatus. A J-tube mercury indicator electrode (IS) and a saturated calomel reference electrode were used. The potentials were read from a L. & E. pH meter, Type 7664. Procedure. From each sample the calcium content was determined by titration with the disodium salt of ethylene glycol bis-( p-aminoethyl ether)-N,A”-tetraacetic acid using ethylene glycol bis-( p-aminoethyl ether) - N , N ’ - tetraacetatomercurate (11) as indicator. Subsequently, with a second aliquot of sample, the sum of calcium and magnesium was determined by titration with the disodium salt of (ethylenedinitri1o)tetraacetic acid using (ethylenedinitri1o)tetraacetatomercurate (11) as indicator. I n each case the following procedure was employed. The samples were taken with pipets from solutions made from standard calcium and magnesium solu-
acidified n-ith hydrochloric acid, gave the following analysis: C 44.07%, H 6.39%, and N 7.30% (Calculated) C 44.21%, H 6.37%, and N 7.37%. Disodium dihydrogen ethylenediamine tetraacetate (EDTA) mas obtained from Versenes, Inc., Framingham, Mass. Both compounds were used without further purification. The disodium salt solutions of the titrants were prepared in strengths of approximately 0.1M and 0.01M and were then standardized against a calcium solution, prepared from primary standard calcium carbonate (Mallinckrodt) . The buffer (0.5M)was made from Eastman N,N’,N”-nitrilotriethanol (pK = 7.8). The proper amount of nitric acid was added to adjust the pH of this buffer to 8.5. One hundredth molar solutions of (ethylenedinitri1o)tetraacetatomercurate(I1) and ethylene glycol bis(flaminoethyl ether)-N,N’-tetraacetatomercurate(I1) were prepared by mixing equivalent amounts of mercuric nitrate and complexing agent. The (ethylene30
20(
w 0 v)
& IOC >
E
C
I oc 3
5
4
7
6
8
9
IO
II
PH
Figure 2. Potential-pH diagram for ethylene glycol bis-(P-aminoethyl ether)-N,N’-tetraacetic acid (Z)system I.
tower limit of electrode potential in certain p H ranges according to HgZ-nHT 2e S Hg’ HnZn-4
+
+
(0.001 M)
+
(0.001M)
111, IV, V, VI. Potential of solutions containing 0.001M MeZ--, 0.001M Me*’+, 0.001M HgZ--, and 0.1 M NaC104 II. Electrode reaction HgO H?O 2e Hgo 20HHa. Potential obtained in a solution containing 0.001M H g - + and 0.1M N,N’,N”-nitrilotriethanol buffer
+
+
+
Table II.
Results of Calcium Titrations in the Statistical Design
hlg. Ca
l:o
1.5 2.5 4.0 6.0 10.0 .-
-0.07 -0.16 -0.57
-0.57 -0.12 -0.30 +0.01
-1.07
-0.11 -0.40
A
Table 111.
Molar Ratio Ca: Mg 1:2 1:s +o. 20 +0.73 +0.16 0.00 -0.10 4-0.37 +o. 22 -0.12 -0.11 -0.11 +o .08 +0.17
1:l + O . 93 +O. 16
Calcium Found,
Dev.,
hlg.
Mg. 1 502 1 517 1 506 1 514 1,514 2.501 2.509 2 509 2 505 2.498 3.985 3 985 4 004 4 023 4 004
%
+0.2 $0 2
.5.948
-1
6 6 6 6
-0
2.505
4.008
6 012
10 020
A
+0.73 -0.28 -0.10 +0.22 +0.08 f0.13
+0.50 -0.01
-0.20 -0.17 -0.11 $0.01
Recovery of Calcium and Magnesium from Standard Solutions
Taken, 1 503
-
1:10
00;
10
9 10 10
10
Table IV.
025 005 025 01 990 01 01 03
-0
to i.0 to
1
0
9 2
0 912
7 $0 7 -0 2 0 -0 -0 -0 -0
Taken, LIg.
0
3
6
6 1 +o 4 -0 1
Dev., w10
0 931 1 839
$2 1 8 4 -1.3
+o +o
4 577 9.00
0
1 ,520 3 040 7 60 15 20
0
2 478 4 883 12 08 2.420
-2 0 -0 4
1
n
1
3 648 7 30
3 692 7 22 18 17 26 60
$1 1 -1 1 -0 4 $0 3
6 12 30 60
-1 8 -0 3 -0 7 +o 4
2
-0 -0 -0 -0
1 3
1 2
I
1 1
2 4 12 24
+0:3 +o 3 -0 4 -0 4
11525
3 047 7 57 15 15
432 86 16 32
+o -0 +o
+o
’
1 824 4 560 9.12
Magnesium Found, Mg.
18 24 36 48 0
6 12 30 60
080 16 40 80
-0 7 -0 5
172 12 18 56
Analysis of Variance for the Calcium Determination
Source of Variance
Sum of Squares
Excess of Rlg Amount of Ca Residual Total
1 049 1 673 1 619
4 341
Degrees of Freedom
Mean Squares
Variance Ratio F
4 4 16
0 262
2 59 4 15
0.418 0.101
Significance 20 5%
57 0
0 24
tions. No pipet smaller than 10 ml. was used. A sufficient amount of N,h”,N”nitrilotriethanol buffer to counteract the effect of acid liberated during the course of the titration and one drop of the corresponding mercury(I1)-complexonate were added. The volume of the solution to be titrated was in each case about 50 ml. Stirring was provided by a magnetic stirrer. The major part of the titrant was added, and about 2 minutes were allom-ed to elapse in order for the solution and electrode t o reach equilibrium. For each voltage reading near the end point about 10 Seconds’ waiting mas necessary. The titration curve was plotted and the inflection point was taken as end point,
For a titrant volume below 10 ml., a 10 ml. microburet was used; for a titrant volume above 10 ml., a 50-ml. buret was used. Determination of Potential-pH Diagrams. The cell consisted of a 50-ml. beaker surrounded by a condensertype jacket connected in turn to a constant temperature bath maintained a t 25.0’ + 0.1’ C. A glass electrode (L. & N. No. 1199-30), a J-tube mercury electrode, and a saturated calomel electrode with an agar bridge were used. About 30 ml. of solution were taken for a measurement and stirred continuously by means of a magnetic stirrer. The pH was varied by droprvise addition of sodium hydroxide or perchloric acid. The pH
was measured with an L. 8: S . pH meter (Type 7661) and the potential by means of an L. 8: K, student potentiometer. Equilibrium Ivithin i l mv. generally was reached in about a minute. The cell was closed with a cork stopper provided with the necessary holes and nitrogen was bubbled through the solution. RESULTS
The titrations of the various samples were designed in a block in order to detect statistically any possible influence of magnesium on the results of the calcium titration with ethylene glycol bis-(P-aminoethyl ether)-h’,N’tetraacetic acid. The arrangement of the block is shown in Table 11. The values listed correspond to the percentage deviation between found and taken values or per cent deviation. In the calculation of these results the titer of the ethylene glycol bis(8-aminoethyl ether)-N,X’-tetraacetic acid solution was derived from the mean obtained in these 25 titrations of standard calcium solutions. Titrations were carried out a t five concentration levels of calcium. For each level, the titrations were in turn carried out with different concentrations of magnesium present. The amount of magnesium is designated as the molar ratio of magnesium to calcium. Therefore the different levels of the magnesium do not correspond in each row to the same absolute amount of magnesium. The single titrations were carried out a t random. Tables I1 and I11 show the results obtained. The result of the analysis of variance is given in Table IV. The presence of magnesium in the range investigated does not have any significant influence on the results obtained for titration of calcium with ethylene glycol his-(@aminoethyl ether) - iY,N’ - tetraacetic acid. However, a variation slightly more significant than 5% between the levels of amount of calcium was found. This was probably caused by the difference in accuracy obtained when various amounts of titrant volume were used. The error for a single calcium titration was found to be =t0.83% with 95% confidence limits, the average error being 1-0.307,. The values found for magnesium were obtained by difference (Table 111). The average error of =k0,7% is about twice as large as the average error in the calcium titration. ACKNOWLEDGMENT
The authors are grateful to J. R. Geigy A.-G., Basel, Switzerland, for the ethylene glycol bis-(P-aminoethyl ether)-N,N’-tetraacetic acid employed for the titrations. This research was supported by the United States Air Force through the Office of Scientific VOL. 29, NO. 2, FEBRUARY 1957
267
Research of the Air Research and Development Command. LITERATURE CITED
(1) Banexitz, J. J., Kenner, C. T., ~ \ & A L . CHEAT. 24, 1186 (1952). ( 2 ) Berkhout, H. IT., Goosens, S . , Chem. Weekblad 4 8 , 3 2 (1952). ( 3 ) Brnnisholz, G., Genton, RI., Plattner, E., Helv. Cham. Acta 36, 782 (1953). (4) Campbell, D. N., Kenner, C. T., A N ~ LCHEM. . 26, 560 (1954).
( 5 ) Cheng, K. L., Kurtz, T., Bray, R. H., Ibid., 24, 1640 (1952). ( 6 ) Diehl, H., Goetz, C. A., Hach, C. H., J . Am. Water W o r k s Assoc. 42, 40 (1950). (7) Flaschka, H., Fortschr. chem. Forsch. 3 , 2 5 3 (1955). (8) Flaschka, H., Huditz, F., Rader Rundschau 2, 181 (1952). (9) Gehrke, C. W.,Affs rung, H. E., Lee, Y. C., A N A L . (?HEM. 26, 1944 (1954). (10) Harvey, A. E., Komarmy, J. hI., Wyatt, G. RI., Ibid., 25, 498 (1953). (11) Holtz, A . H., Chem. Weekblad 47, 48 (1951).
Pribil, R., “Komplexometrie,” Chema 01, Prague, 1954. Reilley, . K,, Porterfield, W. W., h A L . CHEST. 28, 443 (1956). Schmid, R. W.,Reilley, C. S . , J . Am. Chem. SOC.78, 5513 (1956). Schwarzenbach, Gerald, “Die ‘komplexometrische Titration,” Ferdinand Enke TTerlag,Stuttgart, 1955. Schwarzenbach, G., Biedermann, W., Bangerter, F., Helv. C h i m Acta
8
29, 811 (1946).
RECEIVEDfor review August 29, 1956. Accepted October 30, 1956.
Detection of Polymorphic Phase Transformations by Continuous Measurement of Electrical Resistance PAUL D. GARN and STEWARD S. FLASCHEN Bell Telephone laboratories, Inc., Murray Hill, N. J.
b Because polymorphic phase transformations are in some cases not detectable b y differential thermal analysis, the continuous measurement of electrical resistance was studied. The method i s useful as a supplement to differential thermal analysis or calorimetry for the detection of crystallographic phase transitions and the determination of melting points. The systems studied had specific conductances ranging from 3 X to lo-‘ ohm-’ cm.-’. The data obtained have been useful in determining phase diagrams. The method should be especially useful at room and lower temperatures, where differential thermal analysis i s not readily accomplished. In addition to its application to the detection of phase transformations by the measurement of discontinuous changes in resistivity, the method i s readily adaptable to the following of reactions involving a continuous resistivity change.
effect from another transition as much as 30” to 40” C. higher in temperature is completely masked. I n the vicinity of 100” C., the driving off of adsorbed water may indicate an endothermal reaction. These deficiencies are not generally serious, but in some cases, the desired information is not obtainable by use of differential thermal analysis. Other supplementary methods of detection of phase transformations have been considered. The simplest method, considering either procedure or apparatus, is the continuous measurement of
electrical resistance of the sample as it is heated or cooled through the transition region. As a material undergoes a phase transformation, the thermal coefficient of electrical resistance changes because of a change in the electronic energy levels or, in some cases, because of a change in the mobility of ions within the lattice (or liquid, in the case of melting), This change of resistance may be detected by the use of a bridge circuit and appropriate recording equipment. Other investigators have measured
K
T
of the temperatures of polymorphic phase transformations is of considerable importance in several fields of research. The most convenient method in general use is differential thermal analysis, but this has not been successful in a few specific problems. The authors’ apparatus is not satisfactory for use below about 150” C. because of the high heat capacity and thermal lag of the furnace. Furthermore, the heat effect from some phase transformations is very large and the resulting endothermic or exothermic peak may be so broad that a thermal HE DETERMINATIOX
268
ANALYTICAL CHEMISTRY
SP
~E’ooi‘v 17r-777’
lOOK LOG
Figure 1. Bridge circuit used in measurement of continuous resistance
