n as H H hence
) ( H  (r) H H
s
s s
Balances on Nonreactive Processes
JKG FKKKSA
Page 8  4
Heats of solution or mixing for an ideal mixture / solution (e.g. gas mixtures
or liquid mixtures of structurally similar compounds, e.g. Paraffins,
aromatics) is usually negligible, the enthalpy of mixtures is approximately
Aqueous solution of strong acids or bases of certain gases (HCl) or solids
(NaOH) heats of solution should be included in energy balance calculations
Data of the heats of solution is given in Perrys Chemical Engineering
Handbook on pp 2201 2204.
Some values of the heat of solution at 25
o
C of HCl(g) and NaOH (s) and the
heat of mixing at 25
o
C of H
2
SO
4
(l) are given in Table B.11, p.653.
i i mix
H n H
Heat of Mixing and Solutions
SKF 2123  Energy Balance
Instructor: Dr Azeman Mustafa
Balances on Nonreactive Processes
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Page 8  5
The heat of solution
and mixing of
HCl(g) and NaOH
(s) and the heat of
mixing at 25
o
C of
H
2
SO
4
(l)
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Page 8  6
Example 17  Prob. 8.82
Use table B11 to determine the specific enthalpy (kJ/mol HCl) of
hydrochloric acid containing 1 mol HCl/5 mol H
2
O at 25
o
C relative to ;
i. HCl(g) and H
2
O(l) at 25
o
C
ii. H
2
O(l) and an infinitely dilute HCl solution at 25
o
C
HCl mol
kJ
64.05 5) (r H 11;  B Table
HCl mol 1
O H 5mol
r
s
2
= =
=
( )
HCl mol
kJ
11.09 75.14 64.05 ) ( H  5) (r H H
mol
kJ
75.14  ) ( H and
mol
kJ
64.05  5) (r H ; 11  B Table
s s
s s
+ = = = =
= = =
SKF 2123  Energy Balance
Instructor: Dr Azeman Mustafa
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Page 8  7
Example 17  Prob. 8.83
Sodium hydroxide (NaOH) is dissolved in enough water to make up a
20% mole % solution. If the NaOH and water were initially at 77
o
F
(25
o
C), how much heat (Btu/Ibm solution) must be removed for the
solution to be at 77
o
F. Assume the process is carried out at
constant pressure. Use table B11 to evaluate
s
20 mole % NaOH (aq)
25
o
C
H
2
O(l)
25
o
C
NaOH (s)
25
o
C Mixing
tank
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Page 8  8
Example 17  Prob. 8.83
Basis : 100 moles of 20% mole NaOH solution
( 20 moles NaOH(s), 80 moles H2O (l)) both at 25
o
C
Thus, Heat must be removed to keep the solution at 25
o
C
NaOH mol
kJ
34.43 4) (r H 11;  B Table
4
NaOH mol 20
O H mol 80
r
s
2
= =
= =
\

=


.

\

(


.

\

+ 
.

\

=
=


.

\


.

\


.

\

= = = =
=
n
NaOH NaOH
34.43 kJ/mol
NaOH
100
0
0
20
80
NaOH(s), 25
o
C
H
2
O(l), 25
o
C
NaOH(aq), 25
o
C
H
out
(kJ/mol) n
out
(mol) H
in
(kJ/mol) n
in
(mol) Substance
Example 17  Prob. 8.83
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Page 8  10
Example 18  Heat of mixing (H
2
SO
4
solution)
What is the specific enthalpy of 80 wt % H
2
SO
4
(aq, 110
o
F) relative to
pure H
2
SO
4
at (77
o
F) and pure water at 32
o
F.
Basis : 1 lbm of 80 wt % H
2
SO
4
(aq, 110
o
F)
( 0.8 lbm H
2
SO
4
(l),77
o
F ; 0.2 lbm H2O (l),32
o
F)
0.8 lbm H
2
SO
4
(l),77
o
F
1 lbm of 80 wt % H
2
SO
4
(aq, 110
o
F)
0.2 lbm H2O (l),32
o
F
SKF 2123  Energy Balance
Instructor: Dr Azeman Mustafa
Balances on Nonreactive Processes
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Page 8  11
Solution to Example 18 Manually
calculated
( ) BTU 121.2 
kJ 10
BTU 10 x 9.486
SO H lbm 0.8
2.2lbm
1000g
SO H 98g
SO H mol
SO H mol
kJ
34.43  1.36) (r H 11;  B Table
1.36
SO H
lbm 98
mol
x lbm 0.8
O H
lbm 18
mol
x lbm 0.2
r
3 
4 
4 2
4 2
4 2
4 2
s
4 2
2
=


.

\


.

\



.

\



.

\

=

.

\


.

\

=
Pure H
2
O (l), 32
o
F
80 wt% H
2
SO
4
(l), 77
o
F
s
H
2
H
H
1
Pure H
2
SO
4
(l), 77
o
F
Pure H
2
O (l), 77
o
F
80 wt% H
2
SO
4
(l), 110
o
F
( ) ( ) BTU 9.0 F 32  77
F lbm
BTU
1.0 O H lbm 0.2 dT C lbm 0.2 H
o
o 2
F 77
F 32
O H p, 1
o
o 2
= 
.

\

= =
\

+ =
+ 
.

\

+
+ 
.

\


.

\

+
=
+ = =
=
( )
lbm
BTU
95.7
solution lbm 1
BTU 16.51 121.2 9
solution lbm 1
H H H
H
2 s 1
=
+
=
+ +
=
Note : Heat capacity for the solution (or dilute solution can be reasonably estimated
using the heat capacity of the pure solvent
SKF 2123  Energy Balance
Instructor: Dr Azeman Mustafa
Balances on Nonreactive Processes
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Page 8  13
H
2
SO
4
H
2
O EnthalpyConcentration Diagram
Table B11 gives heat of mixing for aqueous sulfuric acid, and heats of
solutions for aqueous solutions of hydrochloride and sodium hydroxide at
25
o
C and 1 atm
Fig. 8.51, p. 399, is an enthalpyconcentration chart for a binary system
involving liquid mixtures of sulfuric acid (ref. states; 77
o
F (25
o
C) & 1 atm
and water (ref. states; 32
o
F (0
o
C) . It
is equivalent to heat of mixing or heat of solution data
can be used to solve energy balance problems for mixing or separation
of aqueous sulfuric acid streams
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Page 8  14
H
2
SO
4
H
2
O Enthalpy
Concentration Diagram
Reference states
H
2
SO
4
(l), 77
o
F (25
o
C) & 1 atm
H
2
O (l), 32
o
F (0
o
C)
SKF 2123  Energy Balance
Instructor: Dr Azeman Mustafa
Balances on Nonreactive Processes
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Page 8  15
H
2
SO
4
H
2
O EnthalpyConcentration Diagram
An H x chart for aqueous solutions of
sulfuric acid at several temperatures.
How to read the figure:
What is the specific enthalpy (BTU/lb
m
)
of a 40 wt% sulfuric acid solution at
120
o
F?
From the figure the reading is about 55
Btu/lb
m
.
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JKG FKKKSA
Page 8  16
Solution to example 18 using H
2
SO
4
H
2
O Enthalpy
Concentration Diagram (Fig. 8.51)
Locate mass fraction
of H
2
SO
4
~ 0.8 (xaxis), move
vertically to ~ 110
o
F line and
then move horizontally
to estimate H (yaxis), hence
H~  96 BTU/lbm
SKF 2123  Energy Balance
Instructor: Dr Azeman Mustafa
Balances on Nonreactive Processes
JKG FKKKSA
Page 8  17
Adiabatic Mixing
Adiabatic mixing is considered to have taken place if substances are mixed
in a wellinsulated system, thus assuming no heat loss to its surrounding (i.e.
Q = 0). This is the condition in which the maximum temperature the product
solution can achieve.
The concentration of product solution can be estimated as follows;
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Page 8  18
Example 19  Adiabatic Mixing
Pure water at 32
o
F is used to dilute 100 mL of 90% wt
H
2
SO
4
(aq, 32
o
F) in a wellinsulated flask. Estimate the maximum
temperature the product solution can achieve, the concentration
of sulfuric acid (wt %), the specific enthalpy of this solution .
Water (32
o
F)
90 wt% H
2
SO
4
(32
o
F)
? wt% H
2
SO
4
(?
o
F)
Q = 0
SKF 2123  Energy Balance
Instructor: Dr Azeman Mustafa
Balances on Nonreactive Processes
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Page 8  19
Example 19  Adiabatic Mixing
From Fig. 8.51 ;
The maximum temp.
~190
o
F, the corresponding
concentration ~ 65 wt%
H
2
SO
4
solution and the
specific enthalpy ~  66
BTU/lbm
190
o
F
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Page 8  20
Working session 16 Problem 8.95 (Modified)
An aqueous solution containing 85% wt H
2
SO
4
at 60
o
F (specific gravity = 1.78) is diluted
with pure liquid water at the same temperature. The feed solution volume is 350 mL.
The mixing may be considered adiabatic and the pressure is constant at 1 atm.
a. The product solution is to contain 30% wt H
2
SO
4
. Calculate the volume (mL) of the
water needed for dilution.
b. Use Fig. 8.51 to estimate the specific enthalpies (BTU/lbm) of the feed solution and
the water & calculate the enthalpy of the product solution and as well as the product
temperature
c. Use Fig. 8.51, estimate the maximum concentration (wt %) of the product solution and
temperature of the product solution that could be achieved by mixing pure water with a
350 mL of 85 wt% H
2
SO
4
solution (both at 60
o
F). How much water is needed.
d. How much heat (BTU) must be removed from the product solution calculated
in part (c) to keep its final temperature in part (c) at 77
o
F?
SKF 2123  Energy Balance
Instructor: Dr Azeman Mustafa
Balances on Nonreactive Processes
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Page 8  21
Working session 16 Problem 8.95 (Modified)
85% wt H
2
SO
4
(aq),60
o
F m
1
kg m
2
kg
350 mL 30 wt % H
2
SO
4
(aq, T
o
F)
H2O (l),60
o
F m
w
kg
a. The product solution is to contain 30% wt H
2
SO
4
. Calculate the volume (mL)
of the water needed for dilution.
( )
( ) mL 1142
L
mL 1000
kg 1
L
kg 1.142 ~ needed water pure of Volume
1.142kg m and kg 1.765 m then , kg 0.623 0.35L
L
kg
1.78 m Given
0.7m m 0.15m : bal. mass O H and 0.3m 0.85m : bal. mass SO H
w 2 1
2 w 1 2 2 1 4 2
= 
.

\



.

\

= = = 
.

\

=
= + =
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JKG FKKKSA
Page 8  22
b. Use Fig. 8.51 to estimate the specific enthalpies (BTU/lbm) of the feed
solution and the water & calculate the enthalpy of the product solution and
as well as the product temperature
( )
lbm
BTU
18.39  F) T (aq, H and
lbm
BTU
27.5
kg
lbm 2.2
x kg 1.142
lbm
BTU
102.5 
kg
lbm 2.2
x kg 0.623 F) T (aq, H
kg
2.2lbm
x 1.765kg Then
0 H m  H m Q : mixing adiabatic for balance Energy
lbm
BTU
27.5 F) 60 (l, H
lbm
BTU
102.5  F) 60 (aq, H
solution feed of enthalpies Specific
o
SO H wt% 30
o
SO H wt% 30
out in
i i i i
o
O H
o
SO H wt% 85
4 2
4 2
2 4 2
=

.

\


.

\

+

.

\


.

\

= 
.

\

= =
= =
From Fig. 8.51, at 30 wt % H
2
SO
4
& H ~  18. 4 BTU/lbm, the product
temperature is about 130
o
F
Working session 16 Problem 8.95 (Modified)
SKF 2123  Energy Balance
Instructor: Dr Azeman Mustafa
Balances on Nonreactive Processes
JKG FKKKSA
Page 8  23
Alternatively, the enthalpy
of the product solution
containing 30% wt H
2
SO
4
and as well as the product
temperature can be
estimated directly from
From Fig. 8.51 ;
The specific enthalpy ~ 
19 BTU/lbm, the product
temp. ~130
o
F
~ 130
o
F
Working session 16 Problem 8.95 (Modified)
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JKG FKKKSA
Page 8  24
c. Use Fig. 8.51, estimate the
maximum temperature of the
product solution that could be
achieved by mixing pure water
with a 350 mL of 85 wt%
H
2
SO
4
solution (both at 60
o
F)
and the concentration (wt %)
of the product solution. How
much water is needed?
From Fig. 8.51 : The maximum
temp. ~ 180
o
F, the
corresponding concentration ~
60 wt% H
2
SO
4
solution and
the specific enthalpy ~  64
BTU/lbm
Working session 16 Problem 8.95 (Modified)
SKF 2123  Energy Balance
Instructor: Dr Azeman Mustafa
Balances on Nonreactive Processes
JKG FKKKSA
Page 8  25
Volume of pure water needed ?
d. How much heat (BTU) that must be removed to keep the final
temperature of the product solution calculated in part (c) at 77
o
F??
( )( ) ( )( )
( ) water mL 260
L
1000mL
kg 1
L
kg 0.2596 m
O H kg 0.2596 m ........
m 0.623
m 0 0.623 0.85
0.60
w
2 w
w
w
= 
.

\



.

\

=
=
+
+
=
Working session 16 Problem 8.95 (Modified)
( ) ( ) ( )
F , O H F , SO H % wt F , SO H % wt
o o o
60 60 85 77 60
2 4 2 4 2
i i i i i i
in
i i
out
i i
H m H m H m
H m H m Q
=
= =
Balances on Nonreactive Processes
JKG FKKKSA
Page 8  26
From figure 8.5.1,
Alternatively, the heat transfer can estimated by the difference between the
enthalpy of the adiabatic solution and that of the solution at 77
o
F.
Working session 16 Problem 8.95 (Modified)
( )
( )
( )
Ibm
BTU
27.5 ~ H
Ibm
BTU
102.5 ~ H
Ibm
BTU
121 ~ H
F O,60 H
F ,60 SO 85wt%H
F ,77 SO 60wt%H
o
2
o
4 2
o
4 2
BTU 110.2 ~ H m H m Q
in
i i
out
i i
=
( ) ( )
BTU 110.7  ~
H m H m H m H m Q
F ,77 SO 60wt%H i i F ,180 SO 60wt%H i i
in
i i
out
i i
o
4 2
o
4 2
= =
SKF 2123  Energy Balance
Instructor: Dr Azeman Mustafa
Balances on Nonreactive Processes
JKG FKKKSA
Page 8  27
NH
3
H
2
O EnthalpyConcentration Diagram
Fig. 8.52, p. 403, is a specific enthalpy of binary mixtures for
liquidvapor equilibria in the ammonia + water system at 1 atm
pressure. It
has saturated liquid and vapor curves plus tie lines in the two
phase region
can be used to solve energy balance problems, such as the flash
vaporization of ammonia + water mixtures
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Page 8  28
NH
3
H
2
O Enthalpy
Concentration Diagram
SKF 2123  Energy Balance
Instructor: Dr Azeman Mustafa
Balances on Nonreactive Processes
JKG FKKKSA
Page 8  29
Enthalpy Concentration Charts
(Vapor Liquid Equilibrium)
An H x chart for ammoniawater
system at 1 atm is shown at several
temperatures.
A tie line is drawn on the enthalpy
concentration chart from x = 0.25 on
the liquid phase to the vaporphase
curve at y = 0.95 at 100
o
F.
The tie line is to determine the
equilibrium composition and the specific
enthalpy of each phase at specified
temperature
Balances on Nonreactive Processes
JKG FKKKSA
Page 8  30
Example 20  prob. 8.98
An NH
3
H
2
O mixture containing 60 wt % NH
3
is
brought to equilibrium in a closed container at 140
o
F.
The total mass of the mixture is 250 g. Use Fig. 8.5
2 to determine the masses of ammonia and of water
in each phase of the system
Liquid phase , L, (~12.9 wt % NH
3
, 87.1 wt% H
2
O)
Vapour phase, V, (80 wt % NH
3
, 20 wt% H
2
O)
( )
lbm 0.164 L lbm 0.386 V
V L 0.55 : bal. Overall
0.8V 0.129L 0.55 0.60 : bal. Ammonia
lbm 0.55
1000g
lbm 2.2
x g 250 mass Total
= =
+ =
+ =
= =
35.1
64.9
140.4
9.65
Vapour
Liquid
H
2
O (gram) NH
3
(gram)
SKF 2123  Energy Balance
Instructor: Dr Azeman Mustafa
Balances on Nonreactive Processes
JKG FKKKSA
Page 8  31
Working session 17  Equilibrium Flash
Vaporization
A 30 wt% NH
3
solution at 100 psia is fed at a rate of 100 lb
m
/h to a
tank in which the pressure is 1 atm. The enthalpy of the feed
solution relative to the reference conditions is 100 Btu/lb
m
. The
vapor composition is to be 89 wt% NH
3
. Determine the temperature
of the stream leaving the tank, the mass fraction of NH
3
in the liquid
product, the flow rate of the liquid and vapor product streams, and
the rate at which heat must be transferred to the vaporizer.
Balances on Nonreactive Processes
JKG FKKKSA
Page 8  32
From the figure
x
V
= 0.89 lb
m
NH
3
/lb
m
T = 120
o
F
x
L
= 0.185 lb
m
NH
3
/lb
m
H
V
= 728 Btu/lb
m
H
L
= 45 Btu/lb
m
100 lb
m
/h
0.3 lb
m
NH
3
/lb
m
H
F
= 100 Btu/lb
m
m
v
lb
m
/h
0.89 lb
m
NH
3
/lb
m
0.11 lb
m
H
2
O/lb
m
H
V
Btu/lb
m
m
L
lb
m
/h
x
L
lb
m
NH
3
/lb
m
(1x
L
) lb
m
H
2
O/lb
m
H
L
Btu/lb
m
Working session 17
SKF 2123  Energy Balance
Instructor: Dr Azeman Mustafa
Balances on Nonreactive Processes
JKG FKKKSA
Page 8  33
Working session 17
L V
F V
m
/h lb 100 x x
x x m
L
=
&
product liquid lb 84
185 . 0 89 . 0
3 . 0 89 . 0
/h lb 100
m m
=

.

\

=
L
m&
( ) product vapor lb 16 /h lb 84  100
m m
= =
V
m&
  Btu/h 5400 Btu/h (100)(100)  (84)(45) (16)(728)
100
= + =
+ = =
F L L V V
H H m H m H Q & &
& &