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Table 10.
1: Summary of Equations for the Gibbs Energy and Related Properties
M in Relation to G MR in Relation to GR ME in Relation to GE

10.9. Excess Properties
V = (∂ G / ∂ P ) T, x (10.4) V R= (∂ G R / ∂ P ) T, x V E= (∂ G E / ∂ P ) T, x
S = − (∂ G / ∂ T ) P, x (10.5) S R= − (∂ G R / ∂ T ) P, x S E= − (∂ G E / ∂ T ) P, x
H = G + TS H R = G R+ T S R H E = G E+ T S E

    
    = G − T (∂ G / ∂ T ) P, x = G R− T (∂ G R / ∂ T ) P, x = G E− T (∂ G E / ∂ T ) P, x
   
   
     
   
 
∂
( G / R
T ) ∂
( G
 

R / RT ) ∂
( G
 

E / RT )
= − R T 2 ________
     
   = − R T 2 __________
        = − R T 2 __________
       
[ ∂ T ] [ ∂ T ] [ ∂ T ]
P, x P, x P, x
CP  = (∂ H / ∂ T ) P, x C
  RP  = (∂ H R / ∂ T ) P, x C
  EP  = (∂ H E / ∂ T ) P, x
  
               
= − T (∂ 2 G / ∂ T 2) P, x = − T (∂ 2 G R / ∂ T 2) P, x = − T (∂ 2 G E / ∂ T 2) P, x
387
410 CHAPTER 11. Mixing Processes
combined enthalpies of 1 mol of pure LiCl(s) and 12 mol of pure H2O(l). Equations for phys-
ical changes such as this are readily combined with equations for chemical reactions. This is
illustrated in the following example, which incorporates the dissolution process just described.
Example 11.3
Calculate the heat of formation of LiCl in 12 mol of H2O at 25°C.
Solution 11.3
The process implied by the problem statement results in the formation from its
constituent elements of 1 mol of LiCl in solution in 12 mol of H2O. The equation
representing this process is obtained as follows:
Li +  _12  Cl  2 → LiCl(s) ΔH  298°   = − 408,610 J

     
       
LiCl(s) + 12H  2O(l)  →  LiCl(12   H  2O)  Δ˜   298  =  −33,614 J
H 
_1
Li+  2  Cl  2 + 12H  2O(l) → LiCl(12H  2O) ΔH  298 °   = − 442,224 J
The first reaction describes a chemical change resulting in the formation of

LiCl(s) from its elements, and the enthalpy change accompanying this reaction is
the standard heat of formation of LiCl(s) at 25°C. The second reaction represents
the physical change resulting in the dissolution of 1 mol of LiCl(s) in 12 mol of
H2O(l), and the enthalpy change is a heat of solution. The overall enthalpy change,
−442,224 J, is the heat of formation of LiCl in 12 mol of H2O. This figure does
not include the heat of formation of the H2O.
Often heats of solution are not reported directly but must be determined from heats of forma-
tion by the reverse of the calculation just illustrated. Typical are data for the heats of formation
of 1 mol of LiCl:4
LiCl( s) − 408,610 J
LiCl ⋅ H 2 O(s) − 712,580 J
LiCl ⋅ 2 H 2 O(s) − 1,012,650 J
LiCl ⋅ 3 H 2 O( s) − 1,311,300 J
LiCl in 3 mol

  
  
  
     H 2 O      
 − 429,366 J 
 
LiCl in 5 mol H 2 O − 436,805 J
LiCl in 8 mol H 2 O − 440,529 J
LiCl in 10 mol H 2 O − 441,579 J
LiCl in 12 mol H 2 O − 442,224 J
LiCl in 15 mol H 2 O − 442,835 J
4“The NBS Tables of Chemical Thermodynamic Properties,” J. Phys. Chem. Ref. Data, vol. 11, suppl. 2,
pp. 2–291 and 2–292, 1982.

11.2. Heat Effects of Mixing Processes 411
Heats of solution are readily calculated from these data. The reaction representing the
dissolution of 1 mol of LiCl(s) in 5 mol of H2O(l) is obtained as follows:
  Li +   _12   Cl 2 + 5H 2 O(l) → LiCl(5H 2 O) Δ H  298°   = −436,805 J

           _
1        
______       LiCl s → Li +   2   Cl 2         ΔH  298
( ) °   = 408,610 J
LiCl(s) + 5 H 2 O(l) → LiCl( 5H 2 O) Δ˜    298 = −28,195 J
H 
˜ , the heat of solution

This calculation can be carried out for each quantity of H2O for which data are given.
The results are then conveniently represented graphically by a plot of ΔH 
per mole of solute, vs. n  ˜ , the moles of solvent per mole of solute. The composition variable,
˜  ≡ n 2 / n 1, is related to x1:
n 
x 2(n 1 + n 2) _____1 − x 1 1
˜  = _________
n      
=         whence x 1 =  _____
    
x 1(n 1 + n 2) x 1 1 + n˜  
˜
The following equations therefore relate ΔH, the heat of mixing based on 1 mol of solution,
and Δ  , the heat of solution based on 1 mol of solute:
H 
Δ˜ 
˜  = ____
ΔH H 
ΔH       = ΔH(1 + n˜ )  or ΔH =  _____   
x 1 1 + n˜  
˜  vs. n˜  for LiCl(s)and HCl(g) dissolved in water at 25°C. Data in
Figure 11.7 shows plots of ΔH 
this form are readily applied to the solution of practical problems.
Because water of hydration in solids is an integral part of a chemical compound, the heat
of formation of a hydrated salt includes the heat of formation of the water of hydration. The
dissolution of 1 mol of LiCl⋅2H2O(s) in 8 mol of H2O produces a solution containing 1 mol
LiCl in 10 mol of H2O, represented by LiCl(10H2O). The equations which sum to give this
process are:
Li +  _12   Cl 2 + 10 H 2 O(l) → LiCl( 10 H 2 O) Δ H  298

°  = −441,579 J
 
LiCl ⋅ 2 H 2 O( s) → Li +  _12   Cl 2 + 2 H 2 + O 2 Δ H  298°  = 1,012,650 J
 
       
        
                     
2 H 2 + O 2 → 2 H 2 O(l) Δ H  298
°   (2)(−285,830) J
  =
LiCl ⋅ 2 H 2 O(s) + 8H 2 O(l) → LiCl( 10 H 2 O) Δ˜   298 = −589 J
H 
Example 11.4
A single-effect evaporator operating at atmospheric pressure concentrates a 15%
(by weight) LiCl solution to 40%. The feed enters the evaporator at a rate of 2 kg·s–1
at 25°C. The normal boiling point of a 40% LiCl solution is about 132°C, and its
specific heat is estimated as 2.72 kJ·kg−1·°C−1. What is the heat-transfer rate in the
evaporator?
412
g)
HCl(
70
60
50
H, kJ per mol of solute

40
s)
LiCI(
30
20
1 2 3 4 6 8 10 20 30 40 60 80 1 02 200 300 400 600 800 10 3
n, moles of H2O per mole of solute
Figure 11.7: Heats of solution at 25°C (Based on data from “The NBS Tables of Chemical Thermodynamic Properties,” J. Phys.
Chem. Ref. Data, vol. 11, suppl. 2, 1982.)
CHAPTER 11. Mixing Processes
11.2. Heat Effects of Mixing Processes 413
Solution 11.4
The 2 kg of 15% LiCl solution entering the evaporator each second consists of
0.30 kg LiCl and 1.70 kg H2O. A material balance shows that 1.25 kg of H2O
is evaporated and that 0.75 kg of 40% LiCl solution is produced. The process is
represented by Fig. 11.8.
1.25 kg superheated
steam at 132 C and
1 atm
Feed at 25 C
2 kg 15% LiCI
0.75 kg 40% LiCI
at 132 C
Figure 11.8: Process of Example 11.4.
The energy balance for this flow process is ΔHt = Q, where ΔHt is the total
enthalpy of the product streams minus the total enthalpy of the feed stream. Thus
the problem reduces to finding ΔHt from available data. Because enthalpy is a
state function, the computational path for ΔHt is immaterial and is selected for
convenience and without reference to the actual path followed in the evaporator.
The data available are heats of solution of LiCl in H2O at 25°C (Fig. 11.7), and the
calculational path shown in Fig. 11.9 allows their direct use.
The enthalpy changes for the individual steps shown in Fig. 11.9 must add to
give the total enthalpy change:

ΔH t = ΔH at  + ΔH bt   + ΔH ct  + ΔH dt  
The individual enthalpy changes are determined as follows:
∙
Δ H at : This step involves the separation of 2 kg of a 15% LiCl solution into its pure
constituents at 25°C. For this “unmixing” process the heat effect is the same as for
the corresponding mixing process but is of opposite sign. For 2 kg of 15% LiCl
solution, the moles of material entering are:
(0.15)(2000)
___________ (0.85)(2000)

      = 7.077 mol LiCl  ___________
         
= 94.366 mol H 2O
42.39 18.015
Thus the solution contains 13.33 mol of H2O per mole of LiCl. From Fig. 11.7
the heat of solution per mole of LiCl for ~n
    = 13.33 is −33,800 J. For the
“unmixing” of 2 kg of solution,

Δ H at  = (+33,800)(7.077) = 239,250 J
414 CHAPTER 11. Mixing Processes
2 kg feed at 25 C
containing 0.30 kg
LiCl and 1.70 kg H 2O
Separation of feed
into pure species Hat
at 25 C
0.30 kg 1.70 kg H2O at 25 C

LiCl at 1.25 kg H 2O at 25 C
25 C
0.45 kg H2O at 25 C
Ht
Mixing of 0.45 kg of
water with 0.30 kg of Hbt
LiCl to form a 40%
solution at 25 C
0.75 kg 40% LiCl at 25 C
Heating of 0.75 kg of Heating of 1.25 kg of

LiCl solution from Hct water from 25 to Hdt
25 to 132 C 132 C at 1 atm
0.75 kg of 40% LiCl 1.25 kg of superheated

solution at 132 C steam at 132 C and 1 atm
FIGURE 11.9: Computational path for process of Example 11.4.
∙
ΔH bt :  This step results in the mixing of 0.45 kg of water with 0.30 kg of LiCl(s) to
form a 40% solution at 25°C. This solution comprises:
0.30 kg → 7.077 mol LiCl  and  0.45 kg → 24.979 mol H 2 O

Thus the final solution contains 3.53 mol of H2O per mole of LiCl. From
Fig. 11.7 the heat of solution per mole of LiCl for ~
   = 3.53 is −23,260 J. Therefore,
n
ΔH bt   = (−23,260)(7.077) = − 164,630 J

∙
ΔH ct : For this step 0.75 kg of 40% LiCl solution is heated from 25 to 132°C. Because
CP is taken to be constant, Δ H ct  = m CP  ΔT,
ΔH ct  = (0.75)(2.72)(132 − 25) = 218.28 kJ = 218,280 J

∙
Δ H dt :  In this step liquid water is vaporized and heated to 132°C. The enthalpy
change is obtained from the steam tables:
ΔH dt   = (1.25)(2740.3 − 104.8) = 3294.4 kJ = 3,294,400 J

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Table 10.

1: Summary of Equations for the Gibbs Energy and Related Properties

M in Relation to G MR in Relation to GR ME in Relation to GE

V = (∂ G / ∂ P ) T, x (10.4) V R= (∂ G R / ∂ P ) T, x V E= (∂ G E / ∂ P ) T, x

S = − (∂ G / ∂ T ) P, x (10.5) S R= − (∂ G R / ∂ T ) P, x S E= − (∂ G E / ∂ T ) P, x

H = G + TS H R = G R+ T S R H E = G E+ T S E

Li +  _12  Cl  2 → LiCl(s) ΔH  298°   = − 408,610 J

The first reaction describes a chemical change resulting in the formation of

pp. 2–291 and 2–292, 1982.

Li +   _12   Cl 2 + 5H 2 O(l) → LiCl(5H 2 O) Δ H  298°   = −436,805 J

˜ , the heat of solution

Li +  _12   Cl 2 + 10 H 2 O(l) → LiCl( 10 H 2 O) Δ H  298

H, kJ per mol of solute

n, moles of H2O per mole of solute

Figure 11.8: Process of Example 11.4.

0.30 kg 1.70 kg H2O at 25 C

0.75 kg 40% LiCl at 25 C

Heating of 0.75 kg of Heating of 1.25 kg of

0.75 kg of 40% LiCl 1.25 kg of superheated

FIGURE 11.9: Computational path for process of Example 11.4.

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Table 10.

1: Summary of Equations for the Gibbs Energy and Related Properties

M in Relation to G MR in Relation to GR ME in Relation to GE

​V = ​(∂ G / ∂ P )​ T, x​​ (10.4) ​V​ R​= ​(∂ ​G​ R​ / ∂ P )​ T, x​ ​V​ E​= ​(∂ ​G​ E​ / ∂ P )​ T, x​

​S = ​− (∂ G / ∂ T )​ P, x​​ (10.5) ​S​ R​= − ​(∂ ​G​ R​ / ∂ T )​ P, x​ ​S​ E​= − ​(∂ ​G​ E​ / ∂ T )​ P, x​

H = G + TS ​H​ R​ = ​G​ R​+ T ​S​ R​ ​H​ E​ = ​G​ E​+ T ​S​ E​

Li + ​ _12 ​​ Cl​ 2​​ → LiCl(s) Δ​H​ 298° ​ ​ = − 408,610 J

The first reaction describes a chemical change resulting in the formation of

pp. 2–291 and 2–292, 1982.

Li + ​ _12 ​ ​Cl​ 2​ + 5​H​ 2​ O​​(​l​)​ → LiCl​​(​5​H​ 2​ O​)​ ​ Δ ​H​ 298° ​ ​ = −436,805 J

​​ ˜ ​​, the heat of solution

Li + ​ _12 ​ ​Cl​ 2​ + 10 ​H​ 2​ O​​(​l​)​ → LiCl​(​ ​10 ​H​ 2​ O​)​ ​ ​ Δ ​H​ 298

H, kJ per mol of solute

n, moles of H2O per mole of solute

Figure 11.8: Process of Example 11.4.

0.30 kg 1.70 kg H2O at 25 C

0.75 kg 40% LiCl at 25 C

Heating of 0.75 kg of Heating of 1.25 kg of

0.75 kg of 40% LiCl 1.25 kg of superheated

FIGURE 11.9: Computational path for process of Example 11.4.

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V = (∂ G / ∂ P ) T, x (10.4) V R= (∂ G R / ∂ P ) T, x V E= (∂ G E / ∂ P ) T, x

S = − (∂ G / ∂ T ) P, x (10.5) S R= − (∂ G R / ∂ T ) P, x S E= − (∂ G E / ∂ T ) P, x

H = G + TS H R = G R+ T S R H E = G E+ T S E

Li +  _12  Cl  2 → LiCl(s) ΔH  298°   = − 408,610 J

  Li +   _12   Cl 2 + 5H 2 O(l) → LiCl(5H 2 O) Δ H  298°   = −436,805 J

˜ , the heat of solution

Li +  _12   Cl 2 + 10 H 2 O(l) → LiCl( 10 H 2 O) Δ H  298