PHYSICAL CHEMISTRY

Temperature and Heat

1. Thermochemistry is the study of energy changes which take
place during chemical reactions.
2. Temperature is the degree of hotness.
3. Molar heat capacity: energy required to raise the temperature
of one mole of the substance by one kelvin or (1
o
C)
4. Specific heat capacity (c): energy required to raise the
temperature of one g of the substance by one kelvin or (1
o
C)
5. The specific heat capacity for water 4.18 J g
-1
K
-1
6.

H = m c T
H = heat absorbed or released
7. When zinc powder is added to plastic cup which contains 50 cm
3
of Cu
2+

(aq) solution, the temperature rises by 6.2
o
C. The specific heat capacity
for Cu
2+
solution is 4.2J g
-1
K
-1
Calculate the heat liberated during the
reaction. [1.302 kJ]
1. Enthalpy Change, H, is given:
The total enthalpy of products - The total enthalpy of reactants

2. Exothermic process: heat given out to surrounding. The
value has a negative sign as the heat content of product is
less than that of the reactant. Define the endothermic
process.


Enthalpy Changes
Energy Level Diagram
1. When one mole of methane is burnt in excess oxygen at a
constant pressure, the heat liberated is 890 kJ. The
thermochemical equation is:
CH
4
(g) + 2O
2
(g) CO
2
(g) + 2H
2
O (l) H

= -890 kJ
mol
-1

2. H

is enthalpy change of reaction under standard

conditions.

a) The total amount of energy released or absorbed is directly
proportional to the number of moles of reactants used.
b) The enthalpy change for the reverse reaction is equal in
magnitude but opposite in sign to the enthalpy change for the
forward reaction.

Thermochemical Equations
Hess's Law
if a reaction is carried out in a series of steps, H for the reaction
will be equal to the sum of the enthalpy changes for the individual
steps
the overall enthalpy change for the process is independent of the
number of steps or the particular nature of the path by which the
reaction is carried out.
Consider the combustion reaction of methane to form CO
2
and
liquid H
2
O
CH
4
(g) + 2O
2
(g) -> CO
2
(g) + 2H
2
O(l)
This reaction can be thought of as occurring in two steps:
In the first step methane is combusted to produce water vapor:
CH
4
(g) + 2O
2
(g) -> CO
2
(g) + 2H
2
O(g) H

= -802 kJ

In the second step water vapor condenses from the gas phase to the liquid phase:
2H2O(g) -> 2H2O(l) H

= -88 kJ
Hesss Law

Combining these equations yields the following:
CH
4
(g)+2O
2
(g)+2H
2
O(g) CO
2
(g)+2H
2
O(g)+2H
2
O(l)
H = (-802) kJ + (-88) kJ= -890 kJ


Determining H for the reaction


is difficult because some CO
2
is also typically produced.
However, complete oxidation of either C or CO to yield
CO
2
is experimentally pretty easy to do:

We can invert reaction number 2 (making it endothermic) and
have CO(g) as a product. (This describes the decomposition of
CO
2
to produce CO and O
2
)


DH = (-393.5 kJ) + (283.0 kJ) = -110.5 kJ
Combining the Equations
C(graphite) + O
2
(g) CO
2
(g) H = -393.5 kJ
C(diamond) + O
2
(g) CO
2
(g) H = -395.4 kJ
C(graphite) C(diamond)

C(graphite) + O
2
(g) CO
2
(g) H = -393.5 kJ
CO
2
(g) C(diamond) + O
2
(g) H = +395.4 kJ

C(graphite) C(diamond) H = +1.9 kJ
1. The standard heat of formation, or standard enthalpy of
formation (represented as H of), for a substance is the
enthalpy change in the formation of 1 mole of that substance
from its individual elements at 1 atmosphere (1 atm) and 25o
C (unless otherwise noted).
2. Elements found in many forms, or allotropes, which have
different heats of formation. To standardize this process, the
allotrope with the most stability is used in determining heats
of formations. The most stable element will always have a
heat of formation = 0.

3. The more negative the value, the more energetically stable the
compound.
Standard Molar Enthalpy Change of Formation
For example, carbon (C) is found as CO, CO2, C(graphite),
etc. However, C(graphite) is the most stable form of C.
Therefore, any heat of formation equation using carbon will
use C(graphite), which is represented for simplicity, as C(s):

C(s) + O
2
(g) CO
2
(g)
C(s) C(diamond)
C(s) + 1/4 S
8
(rhombic) CS
2
(l)
C(s) + Ca(s) + 3/2 O
2
(g) CaCO
2
(s)
Example #1:
Which of the following equations represents a reaction that
provides the heat of formation of ethanol (CH
3
CH
2
OH)?

A) CH
2
= CH
2
(g) + H
2
O(l) CH
3
CH
2
OH(l)
B) 2C(s) + 6 H(g) + O(g) CH
3
CH
2
OH(l)
C) 2 CO
2
(g) + 6 H
2
(g) CH
3
CH
2
OH(l) + 3H
2
O(l)
D) 2 C(s) + 3H
2
(g) + 1/2 O
2
(g) CH
3
CH
2
OH(l)
E) 2 CO(g) + 3 H
2
(g) CH
3
CH
2
OH(l) + 1/2 O
2
(g)

Equation A:
CH2 = CH2(g) is not the most stable form of C, and H2O(l) is not the
most stable form of H or O (C(s), H2(g) and O2(g) are).

Equation B:
H(g) is not the most stable form of H (H2(g) is).

Equation C:
CO2(g) is not the most stable form of C or O (C(s) and O2(g) are).

Equation D:
Correct.

Equation E:
CO is not the most stable form of C (C(s) is).

Example #2:
The heat of formation of CO2(g) is -394 kJ/mole and that of
H2O(l) is -286 kJ/mole. The heat of combustion of C5H12 is -
3534 kJ/mole. What is the heat of formation of C5H12?
C
5
H
12
(l) + 8 O
2
(g) 5 CO
2
(g) + 6 H
2
O(l)


Calculate the heats of formation and combustion for the individual elements
of the reaction:
H
o
c
C
5
H
12
= 1 x (-3534) = -3534 kJ/mole
H
o
f
O
2
= 8 x 0 = 0 kJ/mole
H
o
f
CO
2
= 5 x (-394) = -1970 kJ/mole
H
o
f
H
2
O = 6 x (-286) = -1716 kJ/mole

(-1970) + (-1716) - H
of
+ 0 = -3534
H
o
f
= -152 kJ/mole
Example #3:
Calculate the heat evolved (kJ) for the reaction of 2.40 g of CH4.
(Atomic weights: C = 12.01, H = 1.008)

CH
4
(g) + 2 O
2
(g) CO
2
(g) + 2 H
2
O (l) H
o
= -890.3 kJ/mole



0.149 x (-890.3) = -133 kJ/mole
1. The heat of combustion, or enthalpy of combustion
(represented as H
o
c
), is the amount of energy released in the
combustion of one mole of a substance.
The standard enthalpy of formation of propyne, C
3
H
4
, is
+185.4 kJ/mole. Calculate the heat of combustion of one
mole of C
3
H
4
. The heats of formation of CO
2
(g) and H
2
O(l)
are -394 kJ/mole and -285.8 kJ/mole respectively.
1) Write out and balance the equation based on the information
given:
C
3
H
4
+ 4 O
2
3CO
2
+ 2 H
2
O H
o
c = -1939 kJ/mole


Standard Molar Enthalpy Change of Combustion
Practice:
1. The standard enthalpy of combustion (in kJ/mol) for ethanol
and ethanal (CH
3
CHO) are -1371 and -1167 respectively.
Calculate the standard enthalpy change for the oxidation of
ethanol to ethanal.
x
CH
3
CH
2
OH + O
2
CH
3
CHO + H
2
O
-1371 -1167
2CO
2
+ 3H
2
O

1. 2,000.0 g of water in calorimeter has its temperature raised 3.0C by an
exothermic chemical reaction. How much heat was transferred? [or 25 kJ]

Q = mcT note: since the temperature increased,
T will be a positive number
= (2000.0 g) 4.184 J g C 3.0C
=25,000 J
or 25 kJ (to the correct number of significant digits)
Simple Calorimeter



Bomb
Calorimeter
1. A weighed sample in a platinum crucible is placed in the bomb.
2. A volume of water sufficient to cover the bomb is added and the entire
apparatus is closed.
3. Pure oxygen is pumped and initial temperature recorded.
4. The sample is ignited. The maximum temperature rise is recorded.
5. The heat capacity of calorimeter is the heat required to raise the temperature
of the whole apparatus by 1 K.
Practice:
1. The combustion of 0.625 g of benzoic acid causes the temperature of the
water in the bomb calorimeter to increase by 1.572 K while the
combustion of 0.712 g of an organic compound causes an increase of
1.54 K. Calculate the standard enthalpy change of combustion of the
organic compound.
[ H

C
benzoic acid is -3230 kJmol
-1
. The RMM for benzoic acid and
organic compound is 122 and 60.]
Solution:
Heat released of burning of acid: 0.625/122 x 3230 = 16.55 kJ

1.572 K 16.55 kJ
1.54 K ? kJ (16.2 kJ) released by burning of organic compound.
Standard enthalpy change of combustion of the organic compound:
16.2 kJ/ no. of mol organic compound =
16.2 /(0.712/60) = 1361 kJmol
-1


1. Enthalpy change when one mole of acid reacts with one mole of alkali to
form one mole of water under standard condition.
2. When strong acid is neutralized by strong base, heat of neutralization is
constant at -57.2 kJmol
-1.
3. H

neut
for diprotic strong acid > -57.1 kJ/mol due to dilution of acid
when alkali is added.
H
2
SO
4
+ NaOH NaHSO
4
+ H
2
O H

neut
= -62.0 kJ/mol
NaHSO
4
+ NaOH Na
2
SO
4
+ H
2
O H

neut
= -71.0 kJ/mol
Average = -66.5 kJ/mol

4. When weak acid or weak alkali is used, further heat change is involved in
ionizing the weak acid. Thus, heat of neutralization is less exothermic
(less negative) than -57 kJ/mol.
Standard Molar Enthalpy Change of Neutralization
1. Enthalpy change when one mole of gaseous atoms is formed
from the element in its standard condition.

This process requires energy (endothermic)
Na (s) Na (g) H
at

= +107 kJmol
-1

Cl
2
(g) Cl (g) H
at

= +242 kJmol
-1


Standard Enthalpy Change of Atomization
1. The first electron affinity: enthalpy change when one
electron is added to each gaseous atom in one mole to form
one mole of x
-1
..
2. The second electron affinity: enthalpy change when one
electron is added to each gaseous anion in one mole to form
one mole of x
-2
.

O (g) + e O
-
(g) H
EA1

= -144 kJmol
-1

O
-
(g) + e O
2-
(g) H
EA2

= + 791 kJmol
-1


The second electron affinity is endothermic because energy
is required to overcome the repulsive force between the
electron and the x
-
.
Electron Affinity
1. The lattice energy: energy given out when one mole of an ionic
crystalline solid formed from its ions.
K
+
(g) + Cl- (g) KCl (s) H
lattice

= -701 kJmol
-1

KCl (s) K
+
(g) + Cl- (g) H
lattice dissociation

= +701 kJmol
-1


2. Factors that affecting the magnitude of lattice energy:
a) The attractive forces between the positive and negative ions
b) The distance between the ions/ ionic radius.

3. a) The larger the charge of the ions, the more exothermic is the lattice
energy
b) The smaller the ionic radius, the more exothermic is the lattice energy
Energy changes in Forming Ionic Substances
1. Consider the reaction between Li and fluorine gas to form lithium
fluoride, LiF. The reaction can take place in several steps:
Atomization enthalpy of metal (in this case lithium)
Ionization enthalpy of metal
Atomization enthalpy of non-metal (in this case fluorine)
Electron affinity of non-metal
Lattice enthalpy

a) Li (s) Li (g) . atomization H
at
= +107 kJ/mol
b) Li (g) Li
+
(g) first ionization H
IE
= +496 kJ/mol
c) F
2
(g) F (g) atomization H
at
= +122 kJ/mol
d) F + e F- (g) .. Electron affinity H
EA
= -349 kJ/mol
e) Li
+
(g) + F- (g) LiF(s) .. Lattice energy H
Lattice
= ??? kJ/mol

f) Li(s) + F
2
(g) LiF (s) enthalpy formation = -411 kJ/mol
Born-Haber Cycle
a) Li (s) Li (g) . atomization H
at
= +107 kJ/mol
b) Li (g) Li
+
(g) first ionization H
IE
= +496 kJ/mol
c) F
2
(g) F (g) atomization H
at
= +122 kJ/mol
d) F + e F- (g) .. Electron affinity H
EA
= -349 kJ/mol
e) Li
+
(g) + F- (g) LiF(s) .. Lattice energy H
Lattice
= ??? kJ/mol

f) Li(s) + F
2
(g) LiF (s) enthalpy formation = -411 kJ/mol

Lattice Energy = -411 (107 +496 +122 -349)
= -787 kJ mol
-1

Practice:
1. Construct a Born-Haber cycle for the formation of Na
2
O and use the data
below to calculate the lattice energy of sodium oxide:

Na(s) Na(g) H

= + 108 kJ mol
-1

Na(g) Na
+
(g) H

= + 496 kJ mol
-1

Na
+
(g) Na
2+
(g) H

= + 4560 kJ mol
-1

O
2
(g) O (g) H

= + 249 kJ mol
-1

O(g) + e O
-
(g) H

= - 141 kJ mol
-1

O
-
(g) + e O
2-
(g) H

= + 798 kJ mol
-1

2Na(s) + O
2
(g) Na
2
O H

= -602 kJ mol
-1


[-2716]
1. The enthalpy change of hydration energy H
hyd
, is the
enthalpy change that takes place when one mole of a gaseous
ion dissolve in water to give an infinitely dilute solution.
2. The enthalpy change of hydration energy H
hyd
is always
negative.
3. a) The smaller the ionic radius, the more exothermic the
hydration energy.
b) The higher the charge of the ion, the more exothermic the
hydration energy.


Hydration Energy
HYDRATED
IONS
1. When an ionic compound dissolves in water, two enthalpy are involved.

a) The ions must be separated into gaseous ions. This requires lattice
dissociation energy, an endothermic process.
b) The gaseous ions interacts with water molecules. Hydration energy
(exothermic) is involved.

Heat of soultion
NaCl (s) (in water) Na
+
(aq) + Cl- (aq)
lattice dissociation energy hydration energy
Na
+
(g) + Cl-(g)

Heat of solutions
1. Decreases down the group:


2. Energy

Solubility of Group 2 Sulphates
BeSO
4
MgSO
4
CaSO
4
SrSO
4
BaSO
4

Solubility 0.34 0.18 0.0047 0.0071 0.00009
Lattice energy
Hydration energy
The hydration enthalpies of the cation decreases rapidly in
magnitude than the lattice energy. Heat of solution become more
positive. Solublity decerases