Studies on Boiling Point Elevation of Water and it’s Correlation with Salt

Concentrations for Application in Evaporator Design

Radha Dasa*, Anupam Mukherjeea, Ishita Sinhaa, Arghyadeep Dea, Kunal Roya, Amalesh Sirkara
a Department of Chemical Engineering, Haldia Institute of Technology, Haldia, West Bengal,
India: 721657

Abstract:- The boiling point of a solution increases with the increase of non-volatile solute
concentration as the vapor pressure of solvent reduces due to addition of solute in it. Thus the
solution need to be heated to a higher temperature in order to get the vapor pressure to become
equal to the external pressure at the boiling point. Experiment shows that the change in boiling
point of the solvent above a solution from that of the pure solvent is directly proportional to the
molal concentration of the solute. Since evaporators dealing with boiling solutions, and in
particular with solutions with non-volatile solutes, any problems related with heat transfer on it
must account for the effect of boiling point elevation in designing the evaporator.

In this experimental studies the boiling point elevations of water due to presence of individual
sodium and potassium salts like NaCl, NaOH, KCl, KNO3 as well as mixtures consisting of both
NaCl & NaOH and KCl& KNO3 have been correlated to salt concentrations and solubility of the
salts. The correlations are based on combination of Clasius-Clapeyran relation with Raoult’s law
considering wide range of salt concentrations from 1.4 to 16 wt. %. The correlation takes care of
two factors namely interaction between the salts and water common ion effect of the cations
together.

Keywords: Boiling Point Elevation; Evaporator Design; Activity Co-efficient; Thermodynamics

*Corresponding Authors: radha.das6@gmail.com, Contact: +91-9434453157 (Radha Das)

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Introduction:-
Several chemical industries deal with operation which include boiling and consecutive
evaporative operations. Boiling and evaporation has antagonistic relationship. More specifically,
higher the boiling point lower is the rate of evaporation. For concentrating a salt solution in
water to recover the salts through evaporation of water followed by crystallisation requires
knowledge of boiling point elevation in order to design an evaporation system. Well, particularly
boiling point elevation is a colligative property, more specifically the boiling point of any
substances is dependent over the quantity of dissolved solutes in it [1]. Generally all the studies
of colligative properties are confined to dilute solutions, assuming it as an ideal solution.
Determination of boiling point elevation of single salts in dilute region is well reported in
literature. The boiling point elevation of any solvent depends greatly on the concentration of the
dissolved particles and the nature of the solvent [2].Several industries dealing with desalination
operation needs exact data for design of desalination devices. Multiple effect evaporators are one
of the most widely used devices in chemical industries used for salt concentrating. Khademi et
al. simulated and optimised such a system which too required boiling point elevation studies [3].
Reports have shown that presence of considerable amount of salts in the solution often creates
fouling and scaling problems in an evaporator [4] [5]. Studies of elevation of boiling point of sea
water has been done previously where chlorinity and respective salinity was taken into
consideration [6]. A vivid thermodynamic study has been conducted over naturally obtained sea
water by Bromley et al. which also facilitated design of desalination devices too [7]. In the
reduction of NOX to nitrogen using ammonia, aqueous solution of urea serves as the chief source
of ammonia . In that case the study of boiling point of the aqueous solution of urea plays a vital
role [8]. Henceforth the behaviour of the boiling solutions can be used to clearly demonstrate
solvent and solution structure . Moreover, it can also be implemented to predict single as well as
mixed salt behaviour in a solution.

In this present work the authors have tried to derive an expression for determination of
boiling point elevation of single salts in dilute region which is based on combination of Clausius-
Clapeyron relation with Raoult’s law. The need for a correlation in the concentrated region for
single salts as well as for mixture of salts is well highlighted in this work.

Experimental Procedure :

According to the weight percent of salt required in water the amount of salt was weighed in a
digital weighing balance. Next, the salt was dissolved in 200 ml of water by stirring in 250 ml

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beaker which was hot at the boiling point of water. Followed by this the beaker was further
heated and when the solution started boiling again the temperature was measured using a digital
thermometer. The corresponding atmospheric pressure was noted with the help of a barometer
kept nearby. In order to have an accurate reading of boiling point, the thermometer was dipped at
different locations inside the beaker and the average temperature was noted down. After the
solution started boiling readings were taken quickly so that negligible amount of water
evaporated thus making sure that salt concentration did not change appreciably.

The above experiment was done for individual salts namely NaCl, NaOH, KCl& KNO3 over a
wide range of concentration i.e. 1.4% to 16% for individual as well as mixed salts. Fig.1 show
the variation of B.P of NaCl solution with different salt concentrations at various pressure. The
figure indicates that B.P increases with the increase of solute percentage in the solution. Similar
behaviour was obtained for other salts (NaOH, KCl & KNO3 ) also.

104

103 1.4%
B.P. of NaCl solution

3.2%
102
6%

101 8%

16%
100

99
98.8 99 99.2 99.4 99.6 99.8 100
B. P of Pure Water

FIGURE 1. Variation of B.P of NaCl solution with salt concentration at different pressure

Mathematical Correlation:-

1. For single salt the following correlation has been used. It is a generalized correlation
because it is valid for any single salt of any concentration and having any solubility.

∆Tb / Tb = a (C/S)α ....................(1)

The above is a dimensionless correlation in which “a” and “α ” are constants having specific
values for a particular salt, which have been determined by plotting

Ln (∆Tb / Tb) Vs ln( C/S) .

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Figure 2 to 5 are plots for individual salts namely NaCl, NaOH, KCl and KNO3 . The plots
represent good linear fit of experimental data good co relation coefficient value .

"NaCl"

-3.0
R-Square(COD 0.9806

-3.5

-4.0
Ln(b/Tb)

-4.5

-5.0

-5.5

-6.0

-3.5 -3.0 -2.5 -2.0 -1.5 -1.0 -0.5

Ln(C/S)

FIGURE 2. Plot of Ln (∆Tb / Tb) Vs ln( C/S) for NaCl salt.

" NaOH"

-3.0

R-Square(COD) 0.98063
-3.5

-4.0
Ln( /T )
b b

-4.5

-5.0

-5.5

-6.0

-3.5 -3.0 -2.5 -2.0 -1.5 -1.0 -0.5

Ln(C/S)

FIGURE 3. Plot of Ln (∆Tb / Tb) Vs ln( C/S) for NaOH salt.

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 "KCl"

-3.0

-3.2
R-Square(COD 0.9811

-3.4
Ln(Tb/Tb)

-3.6

-3.8

-4.0

-4.2

-4.4

-5.5 -5.0 -4.5 -4.0 -3.5 -3.0

Ln C/S

FIGURE 4. Plot of Ln (∆Tb / Tb) Vs ln( C/S) for KCl salt.

"KNO3"

-3.0

R-Square(COD) 0.98931
-3.2

-3.4
Ln(Tb/Tb)

-3.6

-3.8

-4.0

-5.5 -5.0 -4.5 -4.0 -3.5 -3.0 -2.5

Ln (C/S)

FIGURE 5. Plot of Ln (∆Tb / Tb) Vs ln( C/S) for KCl salt.

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 2. For double salts the following correlation has been used:


Tbm / Tb = (xA ) 1 (TbA / Tb ) + (xB ) 2 (TbB / Tb )
 
 (2)

Where xA and xB re mole fractions of salt A and salt B based on total salt concentration. (∆TbA/
Tb ) and (∆TbB/ Tb ) are to be obtained from single salt experimental data and corresponding
correlation given above.

Here, it is assumed that since partial pressure of water changes with temperature due to salts
exerting their own vapour pressure and since P OH2O is a function of temperature, ΔPH2O can be
expressed empirically as a direct function of Boiling Point Elevation ΔTm for a mixture of salts.

Derivation of the above equation is based on assuming non - ideal solution [ Ref]. and vapour
pressure correlation of individual salts as follows:

PH2O = PH02O − PH2O = PAv xA1 + PBv xB 2 (3)

In equation (3) in the R.H.S, instead of using γA.xAPA and γBxBPB where γA and γB are activity
coefficients and function of xA and xB and such functions being not found in the literature of
inorganic salts, γA.xAand γBxB have been represented as

(x A ) 1
and ( x B )
2

for simplicity of obtaining a correlation w.r.t mole fractions x A and xB where γ1 and γ2 are
constants for salt A and salt B respectively.

Dividing both sides of above equation by the boiling point Tb of solution and using vapour
pressure correlation w.r.t temperature one gets the following:

Tm  (TbA ) 1  (TbB ) xB 2

 
 = xA + ...........(4)
Tb Tb Tb

 ( PT − p H 2O )Tm
=  .Tm
PAv = f (TbA )
= f1 (TbA − Tb ) =  (TbA )


Similarly, PBv =  (TbB )



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Equation (4) can be simplified to the following form :

Tm  TbA  1  TbB   2

=   x A +   xB ..........(5)
Tb  Tb   Tb 

The final form of boiling point elevation correlation (Equation 5) has been obtained from
equation (3) after making a few assumptions to get to the final form. Here, the basic
manipulation done to equation (3) & (4) through certain assumptions is bit arbitrary, although
logical. Essentially, the effect of temperature on vapour pressure of salts and the non-ideality i.e.
activity coefficient have been clubbed together into the final form (Equation 5) which is a simple
correlation that will have great utility in designing multiple effect evaporators where more than
one salt is present.

Procedure for evaluation of γ1 and γ2 is as follows :

Initially, a value of γ1 was assumed and next γ2was calculated for all the cases corresponding to
BPE for each case. Next a mean γ2 was calculated and corresponding to this mean γ2 , percentage
errors in BPE were calculated for each individual cases. Like this calculations were done for
other γ1 values and finally the one which gave minimum range of error for individual cases was
the case to be chosen to be appropriate. Similarly, γ2 was assumed and next γ1 was calculated for
each case. Next, a mean value of γ1 was calculated and corresponding to this γ1 , percentage
errors in BPE were calculated for each case.

Results and Discussion:

It was noted that in all the four cases (NaCl, NaOH, KCl, KNO3) boiling point elevation
increases with salt concentration over the whole range of concentration.

For double salts Table 1 and 2 give the values of γ1 and γ2 respectively for the two pairs
mentioned above for both dilute and concentrated regions. A single correlation for both the
ranges was found to be not good,

because of variation in degree of non-ideality which is a function of concentration of salts. Also,

how good the correlation is evident from percentage errors between experimentally determined
ΔTm/Tb Vs that predicted by the correlation.

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In Table 1 for set I, γ1 values were assumed and mean γ2 was calculated and the corresponding
range of errors are shown. Similarly, in Table 2, γ2 values were assumed and mean γ1 was
calculated and the corresponding range of errors.

TABLE . 1. Percentage error in prediction of BPR for various composition for assumed value of γ1
(A is KCl , B is KNO3)

Concentration Salt Composition Assumed Calculated mean Calculated Mean %

(% A + % B) Values of Values of γ2 ΔTm/Tb error
γ1
Set-1 1.4 +1.6 0.1 0.06125 0.0216 0.0134
Dilute region 1.6 +1.4 0.0233
1.4 +3.2 0.0245
3.2 +1.4 0.0272
1.4 +1.6 0.2 0.0157 0.0236 0.0015
1.6 +1.4 0.0225
1.4 +3.2 0.0266
3.2 +1.4 0.0255
1.4 +1.6 0.4 -0.016 0.0252
1.6 +1.4 0.0218 -0.0001
1.4 +3.2 0.0282
3.2 +1.4 0.0232
1.4 +1.6 0.5 -0.022 0.0256 0.001
1.6 +1.4 0.0216
1.4 +3.2 0.0286
3.2 +1.4 0.0226
Set-II 1.4 +8 0.1 0.09406 0.0305 0.0226
Concentrate 8 +1.4 0.0354
region 1.4 +16 0.0352
16 +1.4 0.0382
1.4 +8 0.2 0.0334 0.0331 0.1511
8 +1.4 0.0440
1.4 +16 0.0374
16 +1.4 0.0486
1.4 +8 0.4 -0.0208 0.0404 -0.0379
8 +1.4 0.0203
1.4 +16 0.0441
16 +1.4 0.0293
1.4 +8 0.5 0.1231 0.0527 0.4985
8 +1.4 0.0415
1.4 +16 0.0608
16 +1.4 0.0436

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 TABLE 2 . Percentage error in prediction of BPR for various composition for assumed value of γ2
(A is KCl , B is KNO3)

Concentration Salt Assumed Calculated Y1 mean Calculated Mean

Composition γ2 Value ΔTm/Tb error %
(% A + % B) of γ1
1.4 +1.6 0.01 0.215 0.188 0.0245 2.9
1.6 +1.4 0.178 0.0235
1.4 +3.2 0.131 0.0275
Set-1 3.2 +1.4 0.226 0.0266
Dilute region 1.4 + 1.6 0.005 0.2523 0.236 0.0242 1.06
1.6 +1.4 0.300 0.0225 7.28
1.4 + 3.2 0.1529 0.0272 -6.01
3.2 +1.4 0.240 0.0251 0.607
1.4+1.6 0.001 0.2997 0.265 0.0244 1.66
1.6 +1.4 0.3288 0.0223 6.1
1.4 +3.2 0.1784 0.0274 -5.35
3.2 +1.4 0.2549 0.0246 -1.3
Set-II 1.4+6.0 0.02 0.199 0.292 0.0295 -4.6
Concentrate 6.0 +1.4 0.197 0.0254 -15.4
region 1.4 +8.0 0.45 0.0352 3.6
8.0+1.4 0.201 0.0279 -15.36
1.4 +16 0.515 0.0395 4.06
16 +1.4 0.189 0.0295 -18.07
1.4+6.0 0.05 0.0798 0.146 0.02878 -7.15
6.0+1.4 0.1569 0.0307 2.5
1.4 +8.0 0.1486 0.0340 0.068
8.0+1.4 0.1639 0.0343 4.2
1.4 +16.0 0.1712 0.0386 1.67
16 +1.4 0.1568 0.0369 2.59
1.4+6.0 0.06 0.055 0.123 0.0284 -8.38
6.0 +1.4 0.146 0.0317 5.66
1.4 +8.0 0.108 0.0335 -1.47
8.0 +1.4 0.1539 0.0355 7.5
1.4 +16 0.128 0.03816 0.42
16 +1.4 0.148 0.0382 6.1
1.4 +6.0 0.04 0.11 0.175 0.0292 -5.78
6.0+1.4 0.169 0.0296 -1.3
1.4 +8.0 0.2025 0.03458 1.7
8.0 +1.4 0.1748 0.03298 -0.03
1.4 +16 0.228 0.0390 2.82
16 +1.4 0.1664 0.03529 -1.97

From the Table 1 it was found that for γ1 value of 0.4 and γ2 value of 0.016 we get the minimum
mean error (-0.0001 % ) in dilute zone ,whereas for γ1 value of 0.4 , and γ2 value of 0.02 and the
mean error was obtained as (-0.037 % ) for KCl and KNO3 mixed salt. It was also observed from
Table 2 that for γ1 value of 0.265 and γ2 value of 0.001 we get the minimum mean error (0.27 %
) in dilute zone where as for γ1 value of 0.175, and γ2 value of 0.04 and the negligible mean error
was obtained as (-0.76 % ) for KCL and KNO3 mixed salt .

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Comparing Table 1 & 2 it may be suggested that value of γ1 and γ2 are 0.4 and - 0.016 may be
accepted for determination of ( ΔTm) value of KCl and KNO3 mixed salt using the developed
model (equation 5) within a very negligible error range.

TABLE 3. Percentage error in prediction of BPR for various composition for assumed value of γ1
(A is NaCl , B is NaOH)
Concentration Salt Composition Values of Mean Values Calculated Mean % of
(% A + % B) γ1 ofγ2 ΔTm/Tb error
Set-1 1.4 +3.2 0.1 -0.1495 0.0300 0.0002
Dilute region 3.2 +1.4 0.0316
1.4 +6.0 0.0367
6.0 +1.4 0.0362
1.4 +3.2 0.2 -0.1692 0.0317 0.0032
3.2 +1.4 0.0308
1.4 +6.0 0.0386
6.0 +1.4 0.0342
1.4 +3.2 0.3 -0.18126 0.0329 0.0035
3.2 +1.4 0.0302
1.4 +6.0 0.0397
6.0 +1.4 0.0327
1.4 +3.2 0.4 -0.18881 0.0336 0.0086
3.2 +1.4 0.0306
1.4 +6.0 0.0409
6.0 +1.4 0.0317
1.4 +3.2 0.5 -0.1924 0.0341 0.0016
3.2 +1.4 0.0297
1.4 +6.0 0.0409
6.0 +1.4 0.0309
Set-II 1.4 +8.0 0.1 -0.111 0.0356 0.0301
Concentrate 8.0 +1.4 0.0388
region 1.4 +16 0.0455
16 +1.4 0.0430
1.4 +8.0 0.2 -0.1648 0.0414 0.0033
8.0 +1.4 0.0380
1.4 +16 0.0512
16 +1.4 0.0391
1.4 +8.0 0.3 -0.1938 0.0329 0.0035
8.0 +1.4 0.0302
1.4 +16 0.0397
16 +1.4 0.0327
1.4 +8.0 0.4 -0.212 0.0475 0.0236
8.0 +1.4 0.0378
1.4 +16 0.0569
16 +1.4 0.0330
1.4 +8.0 0.5 -0.223 0.0489 0.0229
8.0 +1.4 0.0374
1.4 +16 0.0583
16 +1.4 0.030

10

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 TABLE 4.: Percentage error in prediction of BPR for various composition for assumed value of γ2
(A is NaCl , B is NaOH)
Concentration Salt Composition Assuming Calculated Mean value of γ1 Calculated Mean
(% A + % B) γ2 γ1 ΔTm/Tb Error
%
Set-1 1.4 +3.2 -0.12 -0.1563 -0.04969 0.0289 9.08
Dilute region 3.2 +1.4 0.0879 0.0372
1.4 +6.0 -0.2321 0.0354
6.0 +1.4 0.10173 0.0439
1.4 +3.2 -0.15 -0.035 0.0399 0.0307 6.30
3.2 +1.4 0.1796 0.0345
1.4 +6.0 -0.1556 0.0374
6.0 +1.4 0.17063 0.0398
1.4 +3.2 -0.17 -0.179 0.1593 0.0321 3.022
3.2 +1.4 0.289 0.0320
1.4 +6 -0.0694 0.0388
6 +1.4 0.2388 0.0358
Set-II 1.4 +8 -0.15 -0.143 0.1335 0.0399 2.37
Concentrate 8 +1.4 0.215 0.0405
region 1.4 +16 0.290 0.0498
16 +1.4 0.172 0.0425
1.4 +8 -0.14 -0.1747 0.068 0.0393 10.99
8 +1.4 0.1931 0.0442
1.4 +16 0.0912 0.0492
16 +1.4 0.1635 0.0473
1.4 +8 -0.10 -0.26 -0.035 0.0363 23.4
8 +1.4 0.1267 0.0506
1.4 +16 -0.141 0.0462
16 +1.4 0.1339 0.0558

Similarly, Table 3 shows that for γ1 value of 0.2 and γ2 value of -0.0149 we get the mean error
percentage is (-0.0002 % ) in dilute zone , whereas for γ1 value of 0.2 , and γ2 value of -0.0165
and the mean error was obtained as (-0.003 % ) for NaCl and NaOH mixed salt.
It was observed in Table 4 that for γ1 value of 0.159 and γ2 value of -0.17 we get the minimum
mean error (3.02 % ) in dilute zone. In the concentrated zone for γ1 value of 0.133, and γ2
value of -0.15 the mean error was obtained as (-0.76 % ) for NaCl and NaOH mixed salt
which is negligible.
Results also indicate that the value of γ1 and γ2 are 0.2 and 0.016 may be accepted for
determination of (ΔTm ) value of NaCl and NaOH mixed salt within a very insignificant error.
It is interesting to note that for both cases value of γ1 is within the range of (0.2-0.4) and γ2 is
-( 0.015 -0.016), which are almost constant within negligible error limit.

11

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Conclusions:
It was observed that in the mixture BPE is directly proportional to concentrations of both the
salts . In this paper useful correlation of BPE as a function of salt concentrations has been
developed for both single salt and two salts mixture. The value of γ1 and γ2 obtained from the
above analysis may be used to find out the (ΔT m ) of the two different mixed salts. The
correlation can be extended to systems containing more than two salts by adding terms i.e.
xC 3 + x D 4 + .... to equation 5. The values of γ1 to γ5 may be find out using suitable computer

programme.

ACKNOWLEDGEMENT
The authors gratefully acknowledge the kind financial support of the Ministry of Human
Resource Development (MHRD), Government of India.

REFERENCES

[1] G. W. Castellan, "Physical Chemistry," vol. 296, Addision-Wesley, 1971357-381.

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[3] M. H. Khademi, M. R. Rahimpour and A. Jahanmiri, "Simulation and optimisation of a six effect evaporator in a
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[4] W. Schmidl and W. J. Frederick, "Current treans in evaporator fouling," The Institute of Paper Science &
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[5] T. M. Grace and W. J. Frederick, "Preventing Calcium Carbonate Scaling in Black Liquor Evaporators," South.
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[6] B. M. Fabuss and A. Korosi, "Boiling Point Elevations of Sea Water and Its Concentrates," JOURNAL OF
CHEMICAL AND ENGINEERING DATA , vol. 11, no. 4, pp. 606-609, 1966.

[7] L. A. Bromley, D. Singh, P. Ray, S. Sridhar and S. M. Read, "Thermodynamic Properties of Sea Salt Solutions,"
AIChE Journal, vol. 20, no. 2, pp. 326-334, 1974.

[8] H. J. Dan and J. S. Lee, "Modeling and measurement of boiling point elevation during water vaporization from
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[9] R. H. Perry and D. W. Green, "eds.," in Perry's Chemical Engineer's Handbook, 7th ed., McGraw-Hill, 1997.

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