)

)
_ .-4
SOLUBILITY POLYTHERM OF TERNARY SYSTEM LiCI-NaCI-H
2
0
E. K. Akopov
Krasnodar Institute of the Food Industry
Translated frorT) Zhurnal Prildadnoi Khimii, Vo!. 36, No. 9,
pp. 1916-1919, September, 1963
Original article submitted March 6,1962
The mutual solubility of sodium and lithium chlorides in aqueous solutions at different temperatures was pre-
viously studied by the isothermal method by Smith at 25 [1]. by B1idin at 40 [2]. by Kindyakov, Kyshtymova and
Rogova at 25,50, and 90 [31, and by Ke-Yuan Khu at 25, 50, 90, and 100 [4].
In this paper we present the experimental data obtained on the mutual solubility of the indicated chlorides in
water from the temperature of cOI1.1plete freezing up to 25, from which data the poly therm of the ternary system
LiCI- NaCl- H
2
0 was constructed.
A
Vllf
VI
VII I V 11
20


NrrCL
c-,
c-,
c-
c-
0 -5.5
-20
-w
-60
-7Z
-80 L..J
30
'--_'---ZL
O
-"'----:Z-'c
0
--'---3-:-':O-- B
Fig. 1. System LiCI-NaCI-H
2
0. A) Temperature, C; B) amount, wt.a/o.
I, II, V. VI. VII, VIII. IX. X, and XII represent the internal sections.
The study \Vas made using the visual-poly thermal method [5]. Supercooling of the solutions was observed,
especially at low temperatures, which made it difficult to establish the temperature at which the first crystals ap-
peared. In these cases the previously described techniques [5] were used.
The c.p. lithium chloride used in the study was recrystallized twice. * The monohydrate was dehydrated by
evaporating its solution in a stream of hydrogell chloride, after which the LiCI was ignited gently.
The analytically pure sodium chloride was dissolved in water and then precipitated by the addition of hydrogen
chloride, after which it \Vas dried and ignited gently.
Double-distilled water was used to prepare the solutions (the compositions are expressed in weight percent).
* Under ordinary conditions the compound crystallizes from water solutions as the monohydrate.
1859
)
The System LiCI-H
2
0 was studied by a number of investigators [6, 7J and also by us [5], using the visual method,
f'tom of complete freezing up to 25. It was found that four hydrates are formed in the system:
LiCI 5H
2
0, LiCl . 3H
2
0, LiCI . 2H
2
0, and LiCI . H
2
0. On the poly therm of the given system the transition points
corresponding to them are found respectively at- 64.5and 31.2<7/0 LiCI,-18 and 38.5% LiCI, 18.5 and 450/0 LiCI, and
98 and 56.7'1" LiCI, while the eutectic point is found at-75 and 24.8% LiC!.
TABLE 1. Characteristics of the Ternary Points in the LiCI-NaCI-H
2
0 System
Point
Composition of
solutions, wt. 0/0
ture, C ---I I
Lie! "aCl H,O
--77.D
-n2
-(i;1.5
-185
+17.5
23.0
24.fi
30.7
38.5
44 . .'1
1.2
1.4
O.:-l
0.2;)
0.2
7;).H
74.0
ml.O
61.25
5:i.0
Solid phases
.rrn Li\.i ;m.,() .;.. j\;ar:l 211
2
0
Lii:J :511.,().1- N-ar:I.21["0 1 Nar:l
Liel LiCI :lll.,() -+ NaCI
LiCI.;1lI:0 .L.LiCl.2U.;O+ !'\nCl
Liel 2H;O LiC[.1I
2
-O f ,"iaCI
The System NaCI-H
2
0 has been studied many times [8). The given sy"ttcm was also studied hy us at tempera-
tures ranging from complete freezing up to 10'. A hydrate of composition NaCl . 2H
2
0 is formed in the system.
According to our data, the eutectic point is found at -21.2 and 23.20/u NaCl, while tile transition point is found
at 0.2 and 25.60/0 NaC!.
Ternary System. To establish the crystallization surface of the poly therm diagram of the given ternary system
we investigated 14 internal poly thermal sections. The crystallization curves of the more characteristic sections are
shown in Fig. 1. The arrangement and direction of the sections in the triangle is shown in Fig. 2.
Section II passes close to the side of the LiCI- H
2
0 triangle, and it was investigated in order to estahlish the
crystallization fields of the lithium chloride hydrates inside the system. However, only a small hranch for the separa-
tion of LiCI . 5H
2
0 was detected in it. This indicates that the field of the other hydrates do not reach the indicated
section. To define the houndaries of the ice, NaCI . 2Hp and LiCl . 5Hp fields more precisely in the vicinity of
the LiCI- H
2
0 side we investigated sections IX, X, XII, and XIII, parallel to the side of the NaCI-LiCl triangle.
The solubility poly therm diagram of the ternary system LiCl-
NaCl-H
2
0 was constructed on the hasis of (he studied sections(Fig. 2).
It consists of eight crystallization firlds: ice, LiCI, NaCI, LiCIH
2
0.
LiCl . 2H
2
0, LiCI . 3H
2
0, LiCI . 5H
2
0 and NaCI . 2HP, which con-
verge into five ternary points, of which one is a eutectic (E), while
the other four are transition points (PI-P4)' The composition and
temperature of these points is given in Table 1.
On the diagram the isotherms Wl'rl' drawn at 10 intervals
")

in the fields of ice and NaCI . 2H
2
0 crystallization, while in the
NaCI field, due to the steep rise in the temperature, only one iso-
therm at 25 was drawn. The soluhility data for the 0 isotherm
are given in Table 2.
- - - Wll
N([[L - - ... Wl
Xl!l
Fig. 2. Solubility poly therm of the system
LiCl-NaCI-H
2
0. E) Eutectic point; P) transi-
tion point. The dotted I ines represent the
interna 1 sections of the system.
1860
The isotherm at 25 (in general, the poly therm of the given
ternary system) does not suppOrt the formation of the binary salt
2NaCl . LiCl . 2H
2
0. the presence of \\'hieh was indicated by
Kindyakov, Kyshtymova and Rogove [3]. The ahsence of the in-
dicated compound Ivas also shown hy Ke-Yuan Khu [4).
It should be mew ioned that the results on the solubility for
the isotherm at 25 (Fig. 1) are in good agreement with the data of
Smith [1) and Ke- Yuan Khu [4], obtained by the isothermal method.
The NaCl crysta Ilization field occupies the major portion
on the poly therm diagram. This is explained by the strong
salting-out ability of LiCl toward NaCl, as a result of which the sOlubility of the latter decreases greatly in the
poresenccllL1f the former.
Among the hydrates the largest field is occupied by NaCI . 2H
2
0; it begins on the NaCI-H
2
0 side and proceeds
as a narrow band to the LiCI-1I
2
0 side.
The fields of the LiCl hydrates occupy a small area, especially the LiCI . 2H
2
0 and LiCI . 3H
2
0 fidds, which
an: so small that they adhere tightly to the side of the LiCI-H
2
0 triangle.
TABLE 2. Solubility Isotherm of the System LiCI- NaCI- H
2
0 at 0
No.
of point
.,
:1
I1
;,
li
7
I'
!I
III
11

__
Imoles -per 100-- i
tmoles of wa ter
\'Jt. "/.
-------------.-. ----1- ---.-----
Liel I :';"CI I 11,0 ! l.iCI I :\uCI
0.1)
1.()
;,.1)
s .,
, .-
1 :l,:I
1 ; .1 J
17.7
Ill.II


til.:1
'" 1.0
2:,.fl
21.li
Ili .. -,

fi.ll
I
I
7:1.7 11.11 111l!!.7
71, I ;'.7(; 111.'t.:!
7:1.11 ' I' !1I1.Kl
7:,.:1 I 'Hi/Ill fi7.;,
/:,.;. . 7:-'.17 I' ",;,.fi7
7.-, , '.!. i !IU.to
7:>.11 I 11111.;,;, I
7; . 11 ! ! :H.lj7

;.!J.1l
I 1 7 I 1 ; .111)
iti7.:! I
171i.(lIi I
!l.11 I
1
!
1
Solid phases
j'\aCI .
;'\a(;1 . :- :\"Cl
:\ttC:(
:\"I:[
LiC\, I., :\u(;1
LiCI
The expl'rimcnta I da ta ohta ined for the LiCI- NaCI- H
2
0 system sho \\IS that chemical interil ction bet\'Jeen
lithium cliloride and sodium chloride does not take place in aqueous solutions, whereas in the molten state they form
two compounds, having a 1 : 1 (LiCI . NaCI) and a 1 : 2 (LiCI . 2NaCl) composition [9,10].
Lithium cilluride also does not enter into chemical reaction \'Jith potassium chloride [5], hut it does react with
rLI hiu i Ulll a nu ccs ium cl iloriues in aqueous solutions to give a series of complexes of the bina ry sa It type [11].
Incidentally, it ,houlu be mentioneu that externally the poly therm diagram of the LiCl-NaCI-H
2
0 system
resembles the poly therm diagram of MgCI
2
-NaCI-H
2
0 [R, 12]. As is known, 'Iithium salts in their properties behave
in many respects lil;e m;lgnesium salts, t which is also manifesteu here.
SUMMARY
1. In stuuying thl' L'quilibrium diagram of the system LiCl-NaCI-H
2
0 in the temperature range from com-
plete frl'ezing up to it was l'stahlished that the salting-out effect of LiCI toward NaCI is so great that the solu-
bility of tile latter is reuuceu substantially when the former is present in the solution.
2. It was establisheu that LiCI does not enter into chemical reactioll with NaCI and KCI in aqueous solutions.
whereas it uoes form a numher of complexes \\'ith the cluoriues of the other all(ali metals, rubidium and cesium.
3. The results obta ineu by us on the ,oluhiIity in the system LiCI- NaCI- H
2
0 at 25, using the visual- poly-
thermal methou, arc in agreement the uata obtaineu by the isothermal method [I, 4].
LITERATURE CITED
1. Handbook on rhe Solubility of Salt Systems [in Russian], Vol. ], p. 38 (1953),
2. V. P. Blidin, DAN SSSR, 88, 457 (1953).
3. P. I. Kindyakov, E. A. Kyshtymova,anu S. T. Rogova, Tr. Moskov. Inst. Tonkoi Khim. Tckhnologii im.
M. V. Lomonosova 2, 22 (1958).
4. Ke- Yuan Khu, 190, 194 (I960).
5. E. K. Akopov, ZhNKh, 7, 385 (1962).
6. N. K. Voskresenskaya a;d 0. K. Yanat'eva, Izv. AN SSSR, Ser. Khim.,.!, 97 (1937).
* Apparently, this is due to the strong hydrating ability of lithium ions.
tin general, like the salts of the alkaline-earth metals.
1861
7. Motcan, Lithium [Russian translation], p. 71, IL, Moscow (1959).
8. V. P. U'inskii and A. F. Sagaidachnyi, ZhOKh,.!, 584 (1931).
9. E. K. Akopov, ZhNKh,.!, 1019 (1956).
10. A. S. Arabadzhan and A. G. Bergman, ZhNKh, 7,2226 (1962).
11. Yu. I. Ostroushko, P. I. Bukhchin et aI., Its Chemistry and Technology [in Russian], p. 58, Publishing
House of the Main Administration on the Utilization of Atomic Energy, Council of Ministers of the USSR,
Moscow (1960).
12. N. K. Voskresenskaya, 321 (1930).
1862
All abbreviations of periodicals in the above bibliography are letter-by-Ietter transliter-
ations of the abbreviations as given in the original Russian journal. Some or all of this peri-
odical literature may well be available in English translation. A complete list of the cover- to-
cover English translations appears at the back of this issue.