The Activity Coefficients of Some Bivalent Metal Nitrates in Aqueous

Abdul Wahab, Sekh Mahiuddin, Glenn Hefter, Werner Kunz, Babak Minofar, and Pavel Jungwirth ... Richard A. Potts , Richard D. Barnes , John D. Corbett...
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June, 1942

1469

ACTIVITYCOEFFICIENTS OF BIVALENT METALNITRATES TABLE XI1

TABLE XI Lowest acid concn. ( N ) necesary for reaction HzS04 HCI

Reducing agent

AszOa HzC201 HzCO C~HBOH

0.0 0.0 7.8 2.0

Order of reaction concerning reducing V" agent

2 1 2 1

0.0 0.0 4.6 2.0

Temp. coeff. in HzS0, solutions

1. 0 3.2 1.6 2.8

1 2

1-0 1

for the oxidation of oxalic acid. The catalytic effect of phosphoric acid seems to be connected with the arsenious oxide and not with the vanadium. Nitric acid is a peculiar and very sensi-

[CONTRIBUTION FROM

THE

t i / , in minutes Accelerator ReducUpper and With, lower final Without accel. in agent Formula concn. ( N ) accel. max. concn. As203 H3P01 0.0225-0.3 ' 182 23 , 2 5 -1.0 HzC~01 M n + + 86.25 18.25 HZCIOI F e + + + . 0 5 -0.5 86.25 440 H?CO "01 .0026-0.02 186 46" ,028 - 0 . 2 5 485 CzHsOH HNOs 32"

pactor of acceleration 7.9 4.7 0.2

4.0 15.1

a The end of the induction period; from this point on the reaction passes very quickly.

tive inductor in presence of formaldehyde and ethyl alcohol. JERUSALEM,

PALESTINE RECEIVED JANUARY 26, 1942

CHEMISTRY DEPARTMENT, AUCKLAND UNIVERSITY COLLEGE]

The Activity Coefficients of Some Bivalent Metal Nitrates in Aqueous Solution at 25' from Isopiestic Vapor Pressure Measurements BY R. A. ROBINSON, JEAN M. WILSONAND H.

In a recent communication' isopiestic measurements have been recorded from which the activity coefficient of calcium nitrate a t 25" has been computed and found to be considerably lower than the activity coefficient of calcium chloride.? It is a matter of some interest, therefore, t o obtain measurements on other nitrates of the alkaline earth metals and similar bivalent metals. We are now able to report results on magnesium, strontium, barium, cobalt, copper, cadmium and uranyl nitrate.

Barium Nitrate Ba(N0s)z

0.1865 ,1899 ,2006 ,2265 ,2490 ,4317 ,5344 ,6440

0.5498 ,5659 ,6681 ,8318 1.043 1.294 1.474 1.583 Strontium

Sr(N0a)z

KC1

Sr(NOd2

0.08822 0.1184 0.4522 ,7331 ,09650 .1290 ,7574 ,09980 ,1330 ,1205 ,1591 ,9450 ,1443 ,1898 1.264 ,2069 ,2723 1.363 ,4088 1.565 ,3125 ,4496 ,5820 1.795

0.8746 ,9118 1.099 1.419 1.871 2.442 2.885 3.145

1.585 1.631 1.662 1.757 2.040 2.065 2.120 2.197

3.144 3.262 3.362 3.600 4.371 4.439 4.609 4.831

Nitrate KCI

Sr(N0a)z

KCI

0.5870 ,9330 ,9666 1.199 1.582 1.700 1.952 2.210

1.872 1.921 2.206 2.446 2.811 2.974 3.498 3.909

2.319 2.3% 2.712 3.014 3.456 3.658 4.314 4.843

(1) R . A. Robinson, THIS JOURNAL, 62, 3130 (1940). (2) R . A. Robinson, Tvans. Favadoy S O C .36, , 735 (1940)

KC1

B a ( N 0 3 ) ~ KC1

Ba(NOa)?

KCl

0.09144 0.1151 0.1450 0.1775 0.3316 0.3743 .1155 ,2184 .2591 ,3598 ,09208 ,4030 ,1194 ,4358 ,1489 ,2240 .2664 ,3961 , 1413 ,1735 ,2899 ,3322 ,4022 ,4434 Cobalt Nitrate KC1

Co(N01)r

KC1

CO(NOd?

KCl

0.1419 ,3293 .4263 .5498 .go28 ,9322 1.445 1.490 1.948

1.137 1.155 1.214 1.223 1.362 1.421 1.477 1.487 1.650

2.009 2.038 2.177 2.203 2.499 2.640 2.767 2.810 3.178

1.760 1.815 1.886 1.935 1.990 2.198 2.244 2.261

3.454 3.587 3.772 3.898 4.033 4.578 4.678 4,738

Cu(N0a)r

KCI

Cu(N0a)z

KCI

Cu(N0s)r

KCl

0.1091 1211 ,1921 ,2333 ,2382 .2585 .30GO

0.1514 ,1820 ,2691 ,3300 ,3383 ,3684 ,1411

0.4241 .5389 ,7310 1.000 1.183 1.390 1.529

0.6132 ,8181 1.150 1.668 2.032 2.442 2.766

1.618 1.701 1.915 2.158 2.283 2.415

2.936 3.136 3.633 4.178 4.501 4.828

Cd(N0a)z

KCl

Cd(N0a)p

KCI

Cd(NOp)i

KCI

0.1134 ,1217 ,1559 ,1975 ,3309 ,4141 ,5345 ,6409

0.1571 .1707 .2190 ,2778 ,4766 ,5061 ,8012 ,9786

0.6730 0.6863 1.041 1.138 1.206 1.267 1.531 1.681

1.031 1.048 1.672 1.848 1.974 2.082 2.597 2.888

1.841 1.873 1.989 2.162 2.315 2.381 2.638

3.201 3.255 3.497 3.824 4.150 4.269 4 810

c O ( NO3)2

0.1022 ,2297 ,2932 ,3715 TABLE I ,5798 CONCENTRATIONS OF ISOPIESTIC SOLUTIONS OF POTASSIUM 5962 CHLORIDE AND BIVALENT METALNITRATESAT 25" ,8645 Magnesium Nitrate ,8881 Molality Molality Molality 1,109 Mg(N0a)g KC1 Mg(NO1)z KCI Mg(NO3)z KC1 0.1322 .1347 ,1430 ,1605 ,1739 .2931 .3517 ,4197

s. AYLING

Capper Nitrate

Cadmium Nitrate

(Concluded)

~ A B L FI

brought into equilibrium with solutions of potassium chloride by the method previously described, the concentrations of the isopiestic solutions being

1 ranyl Nitratr 1\/IOldllty 1 ' 0 ? ~ N 0 ~ ) 2 KCI

CJ

hlolality KCI

hIolality

T i 0 (NOa)

KCI

1 O.(NOdq

o 7557 I ,378 1681 0 8650 1 026 3833 1 020 1 999

09:10 7156 2492

2865 2982 4797 3,j1(,

4441

4627 7920

y3;0

1173

titid?

251

1 219

2 525

1 332

3 ,599

' 654 697

li 715

xx;

1.381

I'W3;i

4801

1 1 759

jc,

$16.3

1457

*

recorded in Table 'Table I1 contains values of the osmotic and actixqty coefficients calc11lated from the experimental results in Table I. The selection of referenct. values €or the activity coefficients a t 0.1 -11 was a matter of some difficulty; provisional value.; were obtained by plotting the osmotic

1 498 3 248 I