S

a
v
i
t
a

P
a
I
I
.
c
o
m
Thermodynamics
(The study of energy changes during chemical reactions)
**Enthalpy change for a reaction is affected by Temperature, Pressure, the
quantities of reactants and the physical state of the reactants and products. Hence
molar enthalpy changes are often used. **
Energy: Is the ability to do work, (Joules). In a chemical system energy is the sum oI the
K
E
and Ep oI the particles in the system.
K
E
: - Due to rotational, vibrational, and translational movements
- The particles in a system have a wide range oI energies, K
E
mv
2
- Depends on temperature oI the system K
E
T
- Represented by the Maxwell-Boltzmann distribution graph below, T1 < T2 :
# OI
Particles
K
E
(kJ)
Ep: -due to the position oI the particles
- The closer the particles the stronger the attraction and the lower the Ep
Heat and Enthalpy
Heat content oI a system is the total amount oI energy (Ek Ep) in a system.
Heat content Enthalpy (oI a system) H
Since there is no way oI measuring all the energies oI all the particles oI a system.
ThereIore by convention, arbitrarily: elements in their standard state at standard
temperature (298K), standard pressure (101.3 kPa) have ZERO enthalpy.
Changes in enthalpy are determined by the equation: AH H
Products
- H
Rreactants
(measured in kJmol
-1
).
T
1
T
2
http://www.xtremepapers.net
S
a
v
i
t
a

P
a
I
I
.
c
o
m
Exothermic and Endothermic reactions
Exothermic:
Ep
R
P
Re
1) AH - (negative)
2) A B energy
3) Temperature increases
4) E
p
(prod) lower than E
p
(reactants)
5) Stability oI products is greater
than that oI reactants
6) SelI-sustaining
7) Bonds in product more stable than
those in reactants, strong bonds made
weak bonds broken.
Endothermic:
P
Ep
R
Re
1) AH (positive)
2) A energy B
3) Temperature decreases
4) E
p
(prod) higher than E
p
(reactants)
5) Stability oI reactants is greater
than that oI products
6) Reaction stops when energy input
stops.
7) Weaker bonds are made: stronger
bonds are broken.
Standard Enthalpy Changes, AH
Enthalpy change is measured in kJ/mol. The enthalpy change Ior a reaction is aIIected by
temperature, pressure, the quantities oI the reactants and by the physical state oI the reactants
and products.
Molar enthalpy change values are used.
O
ReIers to a mole oI substance reacting under the standard conditions oI 298K
(25
o
C) and 101.3kPa The chemicals should be in their standard state, and the most
stable state at 298 K, example H
2
O
(l)
, CO
2(g),
C
(graphite)
AH
o
ReIers to enthalpy change measure under standard conditions.
AH
formation
The enthalpy change when one mole oI a compound is Iormed Irom
elements in their standard state:
C
(graphite)
Ca
(s)
3/2 O
2(g)
CaCO
3(s)
AH
(I)
o
-120 kJmol
-1
AH
o
atomisation
Standard enthalpy oI atomization, when one mole oI atoms are Iormed
Irom the element under standard conditions. (gaseous state)
H
2(g)
H
(g)
AH
o
(a)
218 kJmol
-1
AH
o
combustion
(in excess O
2, complete combustion
)
AH
o
neutralisation
Strong Acid Strong Base: H

OH

O AH

-56.7kJmol

Weak Acid Weak Base: = (not -56.7kJmol

Why?)
AH
o
hydration
Or solution enthalpy. When 1mole oI an ionic compound is dissolved in
an excess oI H
2
O
(l)
(relate to lattice energy)
S
a
v
i
t
a

P
a
I
I
.
c
o
m
Bond Enthalpy or Bond Dissociation Enthalpy: X-Y
(g)
X
(g)
Y
(g)
AH
o

C
(g)
C
(g)
4 H
(g)
Mean/Average Bond Enthalpv Jalue calculation for the CH bond.
425 kJmol
-1
70 kJmol
-1
416 kJmol
-1
335 kJmol
-1
1646 kJmol
-1
/4
413 kJmol
-1
ThereIore the average amount oI energy needed to break a C-H bond in all types oI
molecules is 413 kJmol
-1
.
Bond enthalpies can be used to estimate AH
o
(rxn)
Note: the value oI enthalpy oI a reaction, AH
o
(rxn), ,
obtained Irom bond dissociation
calculation is not as accurate as the enthalpy value calculated using Hess`s Law.
First Law of Thermodynamics:
**Energy can not be created or destroyed, enthalpy only transIormed Irom one Iorm to
another. **
Calorimetry: when a reaction is carried out in a calorimeter, (a container used to detect and monitor
changes in temperature during reaction), heat changes are measured during the reaction.
Q
gained/lost by reacting system
Q
lost/gained by the calorimeter and its contents
Changes in heat contents are calculated using:
1. Q AH mcAT c speciIic heat capacity, (J/g
o
C)
2. AH Q n number oI mols used in reaction
n
Heat capacity: C Q/AT (J/
o
C) Molar Heat capacity: C Q/AT(n) (J /
o
C mol)
The most accurate measurements oI heat changes are measured by Bomb Calorimeter:
where known masses are burnt in an excess oI oxygen.
Hess`s Law:
DeI: Enthalpy change in a chemical reaction depends only on the initial and Iinal states
and is independent oI the reaction pathway. (Enthalpy is a 'state Iunction)
Manipulation of equations:
1) reverse an equation: AH sign reversed
2) Multiply by n, divide by n. ThereIore multiply or divide AH by the same Iactor.
AH
o
rxn
_AH
o
f (prod)
- _AH
o
f (react)

II AH
rxn
(negative), then the reaction is spontaneous, products predominate.
S
a
v
i
t
a

P
a
I
I
.
c
o
m
Bond Energies: can be used to estimate AH
o
rxn
kJ/mol
AH
o
rxn
_D (reactants, bonds broken) - _D (products, bonds formed)
C C (OO) 2|OCO| 3(H-O-H)
Bonds broken: C-C, 6(C-H), OO Bonds Iormed: 4 CO, 6 O-H AH
o
rxn
?
Discrepancy Irom AH
o
(Hess`s Law) and Bond Energy calculation is due to the mean/average
bond enthalpies relating to gaseous state oI H
2
O
(g)
while AH
o
relate to the standard state (298 K
/101.3kPa), i.e. H
2
O
(l).
Eurther due to the Iact that values oI bond dissociation are MEAN,
(average), and are not obtained by direct measurements
Entropy and Gibbs free energy:
Entropy: a measure oI the disorder oI molecules,
-A measure oI number oI ways energy in a system can be distributed.
Entropy:
Exothermic reactions are product orientated since Ep oI a system decreases.
So why then do endothermic reactions occur? (Entropy of the system is increasing)
Eacts about Entropy:
-entropy oI elements is not zero.
-A crystal lattice at OK has perIect order, and zero entropy.
-Entropy increases with Temperature
-Entropy increases with molar mass
-Entropy increases with the complexity oI molecules
-increases as L
E
eg: NaI ~NaE
-increases with state s l g
-units oI entropy: J/ 0C
To calculate the entropy change of a reaction:
AS
rxn
_ S
o
(products) - _S
o
(reactants)
II the AS
o
is positive, then the reaction will be spontaneous, product orientated.
Eactors that Iavour reaction are:
COOL (exothermic reaction) CHAOS (increase in disorder).
S
a
v
i
t
a

P
a
I
I
.
c
o
m
Gibbs Free Energy: energy available to do work.
When a system transIers energy to the surroundings some oI this energy is available to do
work. This energy is called 'Iree Energy Gibb`s Iree energy.
AG AH - TAS
AG Iree energy available to do work
AH total energy transIormed between system and surroundings (negative in exothermic
reactions)
AS energy used in rearranging the system the one likely to increase especially at high
temperatures.
ThereIore Ior spontaneous reactions: AG negative
|Limitations oI G: There are many reactions Ior which G is negative and which should
thereIore go spontaneously at room temperature, example combustion oI Iuels, however these
reactions are observed not to happen spontaneously. This is because they have a high activation
energy. Hence, G values provide inIormation only about the thermodynamic or energetic Ieasibility
oI a reaction and not about kinetic stability, the reaction rate is too slow. Activation energy, (this is
independent oI G), provides inIormation about kinetic stability oI a reaction.|
Changes of state: AG 0 .: AH - TAS 0
Hence, the temperature at which the reaction is likely to occur may be determined.
To calculate the Gibb`s Eree energy Ior a reaction:
1. We can manipulate given equations in the same way as Ior enthalpy calculations.
2. We may also use: AG
o
_AG
o
f
(products) - _AG
o
f
(reactants)
Conditions Ior predicting spontaneity oI a reaction
H

Reaction
exo (-) increases () - product-Iavoured
endo() decreases (-) reactant-Iavoured
exo (-) decreases (-) ? T dependent
endo () increases () ? T dependent
Eree Energy and the Equilibrium Constant
The extent oI a reaction can be determined by looking at its equilibrium constant. There is a simple
relationship between the equilibrium constant, K, and G

: G

- RT ln K
A large -ive G means that K Ior the reaction is a large +ive value, indicating that the reaction goes leIt
to right. A large +ive G means that K Ior the reaction is a very small value, indicating that the reverse
reaction is predominant. II G is neither small nor large, more oI an "equilibrium" situation exists.
Eree Energy and Electrode Potential
The potential oI a cell is related to the change in Iree energy that accompanies the cell reaction:
G
0
- n F
0 00 0
n is the number oI moles oI electrons transIerred during the cell reaction;
E is the value oI the Earaday constant (96 487 C),

0
is the emI in volts
Recall that Ior a spontaneous reaction the Iree energy decreases or G is negative. ThereIore
0
must be positive.