MIXING AND SOLUTION

 two different liquids are mixed

 a gas or solid is dissolved into a liquid

 bonds broken between neighboring molecules

 new bonds formed between neighboring molecules or ions in

product solution

 net release (exothermic)/gain in energy (endothermic)

 HEAT OF MIXING (DĤm) AND
SOLUTIONS (DĤs)
 Ideal mixture/solution (gas or liquid mixtures of structurally similar
compounds, obeys Raoult’s law)

 Heat of solution/mixing = negligible

ˆ
ΔH mix   i i
n ˆ
H

 aqueous solution of strong acids or bases of certain gases (HCl) or solids

(NaOH)
 Heat of solution/mixing included in energy balance

 heat of solution at 25oC of HCl(g) and NaOH (s) and the heat of mixing at
25oC of H2SO4(l) are given in Table B.11
HEAT OF MIXING & SOLUTIONS
HEAT OF MIXING & SOLUTIONS
HEAT OF SOLUTION (DĤs) /MIXING
(DĤm)
1 mol pure H2SO4 (l)
ToC. P
Mixing
tank H2SO4(aq)
r moles H2O(l) ToC, P
ToC, P

ĤS H H 2 SO4 ( aq )   H H 2 SO4 (l )  H H 2O (l ) 

Q  H
 
HEAT OF SOLUTION (DĤs) /MIXING
r mole liquid solvent
(DĤ m)
ToC, P liquid solution
1 mol liquid solute ToC, P
ToC, P

Enthalpy of a solution (or mixing) containing r moles H2O/mole solute

 reference states of pure solute and solvent at 25oC and 1 atm

ˆ r 
ˆ  ΔH
H s
 reference states of pure solvent and an infinitely dilute solution at
25oC and 1 atm
Example

Sodium hydroxide (NaOH) is dissolved in enough water to make up a 20% mole

% solution. If the NaOH and water were initially at 77oF (25oC), how much heat
(Btu/Ibm solution) must be removed for the solution to be at 77oF. Assume the
process is carried out at constant pressure. Use table B-11 to evaluate DĤs
Perry’s Chemical Engineering Handbook on pp 2-184 / 2-185
Specific Gravity of Sulfuric Acid
Example 8.5-1
Hydrochloric acid is produced by absorbing gaseous hydrogen chloride (HCl) in
water. Calculate the heat that must be transferred to or from an absorption unit if
HCl(g) at 100oC and H2O(l) at 25oC are fed to produce 1000 kg/h of 20.0 wt. %
HCl(aq) at 40 oC.
Ans: -3.35 x 105 kJ/h
 ENTHALPY CONCENTRATION CHART FOR
H2SO4 - H2O

H = 0 for
pure liquid water at 32F

H =0 for
pure H2SO4 at 77F

Pure H2SO4
Pure water
Example 8.5-2
A 5.0 wt % H2SO4 solution at 60 oF is to be concentrated to 40 wt. % by evaporation of
water. The concentrated solution and water vapor emerge from the evaporator at
180oF and 1 atm. Calculate the rate at which heat must be transferred to the
evaporator to process 1000 Ibm/h of the feed solution.
Ans: 984,000 Btu/h
ADIABATIC MIXING
Example 8.5-3
Pure water at 60 oF is mixed with 100 g of an aqueous 80 wt. % H2SO4. solution, also at
60 oF. The mixing vessel is insulated well enough to be considered adiabatic.
1. If 250 g H2O is mixed with the acid, what will the final solution temperature be?
Ans: 100 oF
2. What is the maximum attainable solution temperature and how much water
must be added to achieve it? Ans: 150 oF,38 g
 ENTHALPY CONCENTRATION DIAGRAM
- Equilibrium composition and specific enthalpy of liquid
and vapor phase
Example 8.5-4
An aqueous ammonia solution is in equilbrium with a vapor phase in a closed system
at 160 oF and 1 atm. The liquid phase account for 95 % of the total mass of the system
contents. Use Figure 8.5-2 to determine the weight percent of NH3 in each phase and
the enthalpy of the system per unit mass of the system contents.
Ans: 8% NH3 (liquid phase), 64% NH3 (vapor phase), 147 Btu/Ibm
Problem 8.96 (3rd Ed.)
ENTHALPY CONCENTRATION DIAGRAM
FOR NH3-H2O
Example 8.5-5
30 wt % NH3 solution at 100 psia is fed at a rate of 100 Ibm/h to a tank in which the
pressure is 1 atm. The enthalpy of the feed solution relative to the reference
conditions used to construct Figure 8.5-2 is 100 Btu/Ibm. The vapor composition is to
be 89 wt % NH3. Determine the temperature of the stream leaving the tank, the mass
fraction of NH3 in the liquid product, the flow rates of the liquid and vapor product
streams and the rate at which heat must be transferred to the vaporizer.
Ans: 120oF,0.185 Ibm/Ibm, 84 Ibm/h, 16 Ibm/h, 5400 Btu/h
 Thermochemistry of
Solution
• Recall Sect. 8.5 : - Heats of solution, Δ
-Hˆ (T, r) change when 1 mol of solute (gas
enthalpy
s
or solid) is dissolved in r moles of a liquid solvent at constant temperature T
• Enthalpy of a solution (or mixing) containing r moles H2O/mole solute for reference
states of pure solute and solvent at 25oC and 1 atm is

ˆ o r 
ˆH  ΔH
s
The enthalpy change associated with the formation of a solution from the solute
elements and the solvents at 25oC is called the standard heat of formation of the
solution. If a solution contains n moles of solvent per mole of solute, then

ΔHˆ  o
f solution 
ˆo
 ΔH f solute
 ΔHˆ o ( r  n)
s
(energy/mole of solute)
• Example : Calculate the standard heat of formation of HCl in 5 mols of water

ΔHˆ  o
f HCl aq 
ˆo
 ΔH 
f HCl g 
 ΔHˆ o (r  n)
s

1
2
1
H 2 g   Cl 2 g   HClg 
2
ΔHˆ 
o
f HCl g 

HClg   nH 2O  HCl (nH 2O) ˆ o (r  n)

ΔH s

5 mol H 2O
r 5
1 mol HCl
ˆo
from table B.1, ΔH f   kJ
HCl g 
mol
 92.31

ˆ o r  5   64.05 kJ
from table B.11, ΔH s
mol
 ΔHˆ 
o
f HCl aq   92.31  64.05  156.36
kJ
mol HCl
• Example : Calculate the standard heat of formation of H2SO4 in an infinitely dilute
solution

ΔHˆ 
o
f H 2 SO4 aq   ˆo
 ΔH f 
H 2 SO4 l 
 Δ ˆ o ( r  n)
H s

r
ˆo
from table B.1, ΔH f  
HCl  g 
kJ
 811 .32
mol
from table B.11, ΔH ˆ o r  5   96.19 kJ
s
mol
 ΔHˆo 
f H 2 SO4 aq    907 . 51
kJ
mol H 2 SO4
(as shown in Table B.1)
• If the standard heat of formation for a dilute solution (i.e. aqueous, r  ∞ ) involved
in a reaction is tabulated (i.e. Table B.1 …. (DHof)solute (aq ) , the tabulated value may be
substituted directly into the expression for (DHor)
o o
(DH f)solution = (DH f)solute (aq)

e.g. : (DHof)NaOH = -469.4 kJ/mol NaOH (DHof)H SO = -907.5 kJ/mol H2SO4

2 4

o
(DH f)(NH4)2SO4 = -1173.1 kJ/mol (NH4)2SO4

• ΔH
The standard
r
o

heat of formation
 
ˆ heat of areaction
Ĥ solution
of the solution
products

involving  
Ĥ solution
solutions
reac tan ts
may be calculated from the standard
(energy/mole of solute)
Example :

2HNO3(aq, r=25) + Ca(OH)2(aq, r= ∞ )  2H2O(l) + Ca(NO3)2(aq, r= ∞ )

ˆ o  2 ΔH
ΔH r  
ˆo
f H 2O ( l )
  
ΔHˆo
f Ca ( NO 3 )2 ( aq )
 
2 ΔHˆo
f HNO3 ( aq )
 
 ΔHˆo
f Ca ( OH )2 ( aq )

• Energy balance

r  sln ˆ sln   n slnΔHˆ sln

ˆ o  n ΔH
Q  ξΔH
out inlet

n sln ΔH sln  n sln  Cp  dT

T
ˆ
Tref sln

Sln = solution
 Thermochemistry of Solution –Problem 9.40

a) Calculate the standard heat of the neutralization reaction between dilute HCl and dilute NaOH solution,
taking the heat of solution of NaCl to be + 4.87 kJ/mol.

HCl (aq, r= ∞) + NaOH (aq, r= ∞ )  NaCl (aq, r= ∞ ) + H2O (l)

ˆ o  ΔH
ΔH r
ˆo
f   H 2O ( l )
 
 ΔHˆo
f NaCl ( aq )
 
 ΔHˆo
f NaOH ( aq )
 
 ΔHˆo
f HCl ( aq )

ΔHˆ 
o
f solution  ˆo
 ΔH f 
solute
 ΔHˆ o (r  )
s

ΔHˆ 
o
f H 2O ( l )  - 285.84 kJ/mol H2O

ΔHˆ 
o
f NaCl ( aq )  [(-411) + 4.87] = - 406.13 kJ/mol NaCl

ΔHˆ 
o
f NaOH ( aq )  [(-426.6) + ( - 42.89)] = - 469.49 kJ/mol NaOH (also available in Table B.1)
ΔHˆ 
o
f HCl ( aq )  [(-92.31) + ( - 75.14)]= - 167.45 kJ/mol HCl
 ˆo
ΔH [ 1(- 285.84) + 1(- 406.13 ) ] – [1(- 469.49) - 1(167.45)] = - 55.03 kJ/mol
r

b) Calculate the standard heat of the reaction between gaseous HCl and solid NaOH to form solid
NaCl dan liquid water,

HCl (g) + NaOH (c )  NaCl (c ) + H2O (l)

ˆ o  ΔH
ΔH r
ˆo 
f H 2O ( l )
 
 ΔHˆo
f NaCl ( c )
 
 ΔHˆo
f NaOH ( c )
 Δ 
Hˆo
f HCl ( g )

ΔHˆ 
o
f solution  ˆo
 ΔH f solute
 ΔHˆ o (r )
s
0 (WHY?)
 ΔHˆ o
f H 2O ( l )  - 285.84 kJ/mol H2O
ΔHˆ o
f NaCl ( c )  -411 kJ/mol NaCl
ΔHˆ o
f NaOH ( c )  -426.6 kJ/mol NaOH
ΔHˆ o
f HCl ( g )  -92.31 kJ/mol HCl

[ 1(- 285.84) - 1(411) ] – [1(- 426.6) - 1(92.31)] = - 177.93 kJ/mol

ˆ 
ΔH o
r
The difference of the standard heat of reaction between (a) and (b) , i.e. 122.9 kJ/mol, because the
former did not involve the standard heat of solution (i.e. DHos(n)).

o o o o
DH s= (DH s)NaCl - (DH s)NaOH - (DH s)HCl
 Thermochemistry of Solution –Problem 9.44

A dilute sulphuric acid solution at 25oC is used to absorb ammonia in a continuous reactor, thereby
producing ammonia sulphate, a fertilizer

2NH3(g) + H2SO4(aq)  (NH4)2SO4 (aq)

a) if the ammonia enters the absorber at 75oC and the sulphuric acid enters at 25oC, and the products
solution emerges at 25oC, how much heat must be withdrawn from the entire unit per mol
(NH4)2SO4 (aq)
H2SO4(aq), 25oC

Basis : 1 mol (NH4)2SO4 (aq)

References : H2SO4(aq), NH3(g) & H2SO4(aq) at 25oC

NH3(g)
75oC
(NH4)2SO4 (aq), 25oC
Energy balance
Q   n i ΔH  i ˆi
ˆ  n ΔH
i
out inlet

ΔHˆ 
i solution 
 Ĥ f  solution,i C 

T

25
p
solution, i
dT

ˆ  ΔH
ΔH i 
ˆ o  ΔH
f i
ˆo
s      C  dT
i
T

25
p
i

ΔHˆ H 2SO 4  -907.5 kJ/mol H2SO4

ΔHˆ NH 3  [-46.19 +  C 

25
75
p
NH 3 ( g ) ] = (-46.19+1.832) = - 44.36 kJ/mol NH3

ΔHˆ  (NH4 )2 SO4

 -1173.1 kJ/mol (NH4)2SO4

Q = DH = 1 (-1173.1 ) – [2(- 44.36 ) + 1(-907.5)] = -176.88 kJ

= - 176.88 kJ/mol (NH4)2SO4 produced

b) Estimate the final temperature if the reactor of part (a) is adiabatic and the product solution
contains 1.00 mole % (NH4)2SO4 . Take the capacity of the solution to be that of pure water (4.184
kJ/mol-oC)

Basis : 1 mol of 1.00 mole % (NH4)2SO4 solution

References : H2SO4(aq), NH3(g) & H2SO4(aq) at 25oC
H2SO4(aq), 25oC

Energy balance
ˆo 
Q  ξΔH r  n ΔHˆ   n ΔHˆ
out
i i
inlet
i i Q=0

ˆo 
ΔH r  ΔHˆ
products
o
f   ΔHˆ
reactants
o
f
NH3(g)
75oC
 C  dT
T
ˆ 
ΔH 1 mole% (NH4)2SO4 (aq), ToC
i p
25 i
 o
(DH f)NH3 = -46.19 kJ/mol NH3

o
(DH f)H SO = -907.5 kJ/mol H2SO4
2 4

o
(DH f)(NH4) SO = -1173.1 kJ/mol (NH4)2SO4
2 4

o
DH = 1 (-1173.1 ) – [2(- 46.19 ) + 1(-907.5)] = -173.22 kJ/mol (NH 4)2SO4
r

Mass balance
2NH3(g) + H2SO4(aq)  (NH4)2SO4 (aq)
mol (solute) : 0.02 0.01 0.01
gram 0.01 mol NH
ˆ o(solution): 4 2 SO 4
0.34 
18.8 19.14kJ 
ξΔH r  x  - 173.22    1.7322 kJ
1  mol NH 4 2 SO 4 
  n ΔHˆ   n ΔHˆ
out
i i
inlet
i i

Take the capacity of the solution to be that of pure water (4.184 kJ/mol-oC)

Enthalpy (inlet)

 C= + 1.832 kJ/mol NH

75
DHNH3 (75oC) = p 3
25 NH 3 ( g )

DHH2SO4 (25oC) = 0 kJ/mol H2SO4

Enthalpy (outlet)
kJ
4.184 o
T  25
DH (NH4)2SO4 (ToC) =
kgkJ/kg
C (NH ) SO (solution)
4 2 4

Balances on Reactive
 Adiabatic reactor , Q = 0

ˆo 
Q  ξΔH r  n ΔHˆ   n ΔHˆ
out
i i
inlet
i i 0

 kJ   kJ 
 - 1.7322 kJ  0.01914 kg NH 4 2 SO 4   4.184 o

 T  25  - 0.02 mol NH 
3 
 1.832 
 kg C   mol NH 3 

Solve the above equation for the product temperature, T = 47.1 oC

In a real reactor, which is imperfectly insulated, some heat will be transferred out of the
reactor and hence the final solution temperature will be less than 47.1 oC