THERMOCHEMISTRY OF SOLUTION

Heats of solution, ΔHˆ (T, r)- elemental species that constitute the
s
reactants and products in the states in which the elements are found at
25oC and 1 atm

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 )
ˆ = ΔH
H s

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 SOLUTION
 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
ENTHALPY CONCENTRATION CHART FOR H2SO4 - H2O
 STANDARD HEAT OF FORMATION OF SOLUTION

o
Elements of Solute 25 C o
Solution 25 C
o
Solvent 25 C

(ΔHˆ ) o
f solution ( )
ˆo
= ΔH f solute
+ ΔHˆ o ( r = n)
s

1
Li + Cl2 ® LiCl( s ) DH 298
!
= -408610 J
2
LiCl( s ) + 12 H 2O(l ) ® LiCl (12 H 2O) ~
DH 298 = -33614 J

1
Li + Cl2 + 12 H 2O( l ) ® LiCl (12 H 2O) DH 298
!
= -442224 J
2
 STANDARD HEAT OF FORMATION OF SOLUTION
Tabulated values of Standard heat of formation for infinitely dilute solution
o
(DH f)solute (aq )) eg in Table B.1

o o
(DH f)solution = (DH f)solute (aq)

Eg.
o
(DH f)NH4OH (aq) = -366.48 kJ/mol H2SO4
o
(DH f)NaOH(aq) = -469.4 kJ/mol NaOH
o
(DH f)H2SO4(aq) = -907.5 kJ/mol H2SO4
o
(DH f)(NH4)2SO4(aq) = -1173.1 kJ/mol (NH4)2SO4
 STANDARD HEAT OF FORMATION OF SOLUTION

Standard heat of reaction involving solutions:

DHˆ ro = å i f i-
n DHˆ o
( ) ån (DHˆ ) i
o
f i
products reactants

Eg.

Energy Balance using Heat of Reaction Method:

DH! = z!DHˆ r" + å n!i Hˆ i - å n!i Hˆ i

out in
Example

Calculate the standard heat of formation of

a) HCl in 5 mols of water . Ans: -156.36 kJ/mol HCl
b) H2SO4 in an infinitely dilute solution. Ans: -907.51 kJ/mol H2SO4
Problem 9.39

Three cubic meters of a 1.00-molar aqueous sulfuric acid solution

(SG = 1.064) is stored at 25oC. Calculate the standard heat of
formation of the solution in kJ/mol H2SO4 relative to the solute
elements and water, and the total enthalpy of the solution relative to
the same reference conditions.
Ans: -884.7 kJ/mol H2SO4, -2.65 x 106 kJ
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.
Ans: - 55.03 kJ/mol
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 ) à NaCl (c ) + H2O (l)

Ans: - 177.93 kJ/mol

Example
1 mol of 15% sulfuric acid is neutralized completely at 25oC
by 10% sodium hydroxide. Calculate the heat released by this
neutralization reaction. The heat of solution of Na2SO4(aq) is
–1.17 kJ/mol. Ans: -22.7 kJ
H2SO4(aq) + 2NaOH(aq) 2H2O(l) + Na2SO4(aq)
 Example : Atomic species balance (Revisit)

100 mol/min C2H6

n1 mol C2H6/min
n2 mol C2H4/min
40 mol/min H2

n1 = 60 mol C2H6/min
n2 = 40 mol C2H4/min
 Example : Atomic species balance
(Revisit)
100 mol/min C2H6 C2H6 à C2H4 + H2
n1 mol C2H6/min
n2 mol C2H4/min
C balance: (input = output) 40 mol/min H2

" mol C 2 H 6 %" 2 mol C % " n1mol C 2 H 6 %"

2 mol C % " n mol C H %" 2 mol C %
$100 '$$ '' = $ '$
$ '' + $ 2 2 4
'$$ ''
# min &#1 mol C 2 H 6 & $# min ' 1 mol C H
&# 2 6& #
min &#1 mol C 2 H 4 &
100 mol C/min = n1 + n2

H balance : (Input = Output )

€ "100 mol C 2 H 6 %" 6 mol H % " 40 mol H 2 %" 2 mol H %

$ '$$ '' = $ '$$ '' +
# min &#1 mol C 2 H 6 & # min &#1 mol H 2 &
" n mol C 2 H 6 %" % " n mol C H %" 4 mol H %
$ 1 '$ 6 mol H ' + $ 2 2 4
'$$ ''
$ min $
' 1 mol C H ' min 1 mol C H
# &# 2 6& # &# 2 4&

600 mol H/min = 80 mol H/min + 6n1 + 4n2

EXAMPLE 9.5-6

Take the heat capacity of sulfuric acid to be 3.85 J/g.oC and the heat
capacity of Na2SO4(aq) to be that of pure water (4.184 J/g.oC).