KIMIA DASAR

VI Thermodinamika dan Termokimia

B.Ellyana, B.Tjandra
Fakultas Teknobiologi
Universitas Surabaya
 Units of Energy
Energy is the capacity to do work SI units: Joules (J)
1 cal = 4.184 J
• Thermal energy is the energy associated
with the random motion of atoms and
molecules
• Chemical energy is the energy stored
within the bonds of chemical substances
• Nuclear energy is the energy stored
within the collection of neutrons and
protons in the atom
• Electrical energy is the energy associated
with the flow of electrons
• Potential energy is the energy available
by virtue of an object’s position
Work involves moving something
 Thermochemistry is the study of heat change in
chemical reactions.
System is object of our study.
SYSTEM
SURROUNDINGS

Surrounding:
Outside the
system

open closed isolated

Exchange: mass & energy energy nothing
Exothermic process is any process that gives off heat – transfers
thermal energy from the system to the surroundings.

2H2 (g) + O2 (g) 2H2O (l) + energy

H2O (g) H2O (l) + energy

Endothermic process is any process in which heat has to be

supplied to the system from the surroundings.

energy + 2HgO (s) 2Hg (l) + O2 (g)

energy + H2O (s) H2O (l)

 Thermodynamics

State function
depends only
on the initial
state and final
state

Potential energy of hiker 1 and hiker 2 is the same even though they took
different paths.
 The First Law of Thermodynamics

The first law of thermodynamics, which is based on

the law of conservation of energy,
states that energy can be converted from one form to
another, but cannot be created or destroyed.

The change in internal energy ΔE is given by

ΔE = Δ Ef - ΔEi

Ei and Ef are the internal energies of the system in

the initial and final states
 Thermodynamics
DE = q + w
DE or ΔU is the change in internal energy of a system
q is the heat exchange between the system and the surroundings
w is the work done on (or by) the system
w = -PDV when a gas expands against a constant external pressure
 Enthalpy

DE = q + w
At constant pressure, q = DH and w = -PDV
DE = DH - PDV
DH = DE + PDV
 Enthalpy (H) is used to quantify the heat flow into or out of a system in
a process that occurs at constant pressure.

DH = H (products) – H (reactants)
DH = heat given off or absorbed during a reaction at constant pressure
 Endotermic

System absorbs heat

Endothermic

DH > 0

6.01 kJ are absorbed for every 1 mole of ice that melts at 00C
and 1 atm.

H2O (s) H2O (l) DH = 6.01 kJ

 Exothermic

System gives off heat

Exothermic

DH < 0

890.4 kJ are released for every 1 mole of methane that is

combusted at 250C and 1 atm.

CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (l) DH = -890.4 kJ

 Thermochemical Equations

• The stoichiometric coefficients always refer to the number of moles

of a substance

H2O (s) H2O (l) DH = 6.01 kJ

• If you reverse a reaction, the sign of DH changes

H2O (l) H2O (s) DH = -6.01 kJ

• If you multiply both sides of the equation by a factor n, then DH
must change by the same factor n.

2H2O (s) 2H2O (l) DH = 2 x 6.01 = 12.0 kJ

 Thermochemical Equations

• The physical states of all reactants and products must be specified

in thermochemical equations.

H2O (s) H2O (l) DH = 6.01 kJ

H2O (l) H2O (g) DH = 44.0 kJ

How much heat is evolved when 266 g of white phosphorus (P4)

burn in air?

P4 (s) + 5O2 (g) P4O10 (s) DH = -3013 kJ/mol

1 mol P4
266 g P4x x -3013 kJ= -6470 kJ
123.9 g P4 1 mol P4
The specific heat (s) of a substance is the amount of heat (q) required
to raise the temperature of one gram of the substance by one degree
Celsius.

The heat capacity (C) of a substance is the amount of heat (q) required
to raise the temperature of a given quantity (m) of the substance by
one degree Celsius.

Heat (q) absorbed or released:

q = msDt
C = ms q = CDt

Dt = tfinal - tinitial
 How much heat is given off when an 869 g iron bar cools from 940C
to 50C?

s of Fe = 0.444 J/g • 0C

Dt = tfinal – tinitial = 50C – 940C = -890C

q = msDt = 869 g x 0.444 J/g • 0C x –890C = -34,000 J

 How is heat of a reaction
measured?
Calorimeter: device used to measure the heat released (or absorbed)
by a physical or chemical process

1) Coffee-cup calorimeter
constant pressure
used to measure heat flow involved in neutralization
reactions; heats of solution or dilutions
 information needed to use this apparatus
heat capacity of the calorimeter
temperature change of the solution
mass of the solution in the calorimeter

No heat enters or
leaves!
2) Bomb calorimeter
constant volume
used to measure heats of combustion

No heat enters or leaves!

qcal  water  qrxn  0
qcal  water  Ccal  water x Dt
qcal  water  10.17 kJ/ C x (25.95 - 20.28)C
qc alwater  57.66 kJ
qc alwater  - qrxn
1.435 g
qrxn  -57.66 kJ / ( )  - 5143.1916 kJ / mol
128 g/mol
qcal  water  qPb  0
qwater  cal  100 x 4.184 J/g C x (23.17 - 22.50)C  280.328 J
q Pb  m x s x Dt
 280.328 J  26.47 g x s x (23.17 - 89.98)C
s  0.1585 J/g. C
 Calculating ΔHo
• The enthalpy change associated with a reaction can be
determined by several methods, depending on the
information provided. These methods include:

1. Stoichiometric calculation, using standard

enthalpies
2. Hess’s Law, using standard reactions of known
ΔHorxn
3. Heats of formation
4. Bond enthalpy calculations
 Stoichiometric Enthalpy Calculations
• Lets take the combustion of hydrogen gas as Enthalpy Diagram
an example of an exothermic reaction.
2H2(g) + O2(g)
2H2(g) + O2(g)  2H2O(g) ΔHorxn= -483.6 kJ/mol

ΔH < 0
1. Enthalpy is an extensive property. The exothermic
magnitude of ΔH is proportional to the amount of
reactant consumed. So, 2 mol of H2 will evolve
-483.6 kJ. 4 mol of H2 will evolve double that.
2H2O(g)
2. Enthalpy of the reverse reaction has the
opposite sign. The decomposition of 2 moles of
H2O into 2 moles of H2 and 1 mole of O2 is +483.6
kJ.

3. The state of the reactants matters. If liquid

water formed instead of steam, ΔH would be
different.
 Example
• Calculate the heat released when 30.0 g of iron(III)oxide is
combined with 15.0 g of Al(s) at 1 bar.

Fe2O3(s) + 2Al(s)  Al2O3(s) + 2 Fe(s) ΔHorxn= -851.5 kJ/mol

• To determine the enthalpy change of the reaction, we must

first determine the moles of the limiting reactant.

mol Fe2 O3
30 g Fe2 O3 x = .376 mol Fe2 O3
159.7 g Fe2 O3
mol Al
15g Al x = .556 mol Al Limiting Reactant
27 g Al

−851.5 kJ heat
.556 mol Al x = −𝟐𝟑𝟕 𝐤𝐉
2 mol Al reacted
Enthalpies of Formation

For pure elements, and for elements in

their most stable form, ΔHof = 0 kJ/mol
 Enthalpies of Formation

• The enthalpy change associated with a the formation of a

molecule is called the enthalpy change of formation, ΔHf (also
called heat of formation).

• For a given reaction, if you know the enthalpies of formation

of the reactants and products:

∆𝐇 𝐨 𝐫𝐱𝐧 = ෍ 𝐧 ∆𝐇 𝐨 𝐟 𝐩𝐫𝐨𝐝𝐮𝐜𝐭𝐬 − ෍ 𝐧 ∆𝐇 𝐨 𝐟 (𝐫𝐞𝐚𝐜𝐭𝐚𝐧𝐭𝐬)

 Element = 0

D f H 0 (C10H8 )  10 x(393,5)  4 x(285,7)  (5156)  78,2KJ / mol

 Practices
• Given the following ΔHorxn values, calculate ΔHorxn for the reaction:
2SO2(g) + O2(g)  2SO3(g)

(1) SO2(g) ---> S(s) + O2(g) ΔHorxn (1) = 296.8 kJ/mol

(2) 2S(s) + 3O2(g) ---> 2SO3(g) ΔHorxn (2) = -791. 4 kJ/mol

It is necessary to multiply reaction (1) by a factor of 2 in order to

get 2 moles of SO2(g) and to cancel out S(s) and 2 moles of O2(g).

(1) 2 [SO2(g) ---> S(s) + O2(g) ] ΔHorxn (1) = 2 (296.8 kJ/mol)

(2) 2S(s) + 3O2(g) ---> 2SO3(g) ΔHorxn (2) = -791. 4 kJ/mol

(3) 2SO2(g) + O2(g) ---> 2SO3(g) ΔHorxn (3) = -197.8 kJ/mol

• Calculate the enthalpy change for the combustion of benzene,
C6H6 to form CO2 and H2O using standard heats of formation.

ΔHf H2O(l) = -285.8 kJ/mol

ΔHf CO2(g) = -393.5 kJ/mol
ΔHf C6H6(l) = 49.1 kJ/mol
 Molar Bond Enthalpies

• The enthalpy change for the complete decomposition of water:

H2 O L → O g + 2H(g)

is ∆𝐻 𝑜 𝑟𝑥𝑛 = + 925 kJ/mol.

• In a water molecule, there are 2 O-H

bonds. The positive value of enthalpy
indicates that heat (energy) must be
absorbed by the system in order to break
these bonds.

• Therefore, we can estimate that the

molar bond enthalpy, Hbond, of each O-H
bond (energy needed to break the bond)
is 463.5 kJ/mol
 Molar Bond Enthalpies

• Breaking bonds requires energy

(Endothermic)
• Making bonds releases energy
(Exothermic)
• Reactants – products this time!
Table of common bond
enthalpies. These are
the energies to break
the bonds. When you
form bonds, the sign of
H will be negative.
 (CH4 + Cl2 ) – (CH3Cl + HCl )
(414 kJ/mol + 243 kJ/mol) - (331 kJ/mol + 431 kJ/mol)

= -105 kJ/mol
This reaction is overall exothermic because the final product is lower
in energy than the reactants.
 Practise

∆H = [ (5 x O=O) + ( 8 x C-H) + (2 x C-C)] – [(3 x 2 x C=O)

+ (4 x 2 x H-O)]

∆H = [(5 x 498) + (8 x 413) + (2 x 347)] – [ (3 x 2 x 805) +

(4 x 2 x 464)]

∆H = -2054 kJ/mol
 Second Law of Thermodynamics

The second law of thermodynamics explains why chemical processes

tend to favor one direction.

If a reaction does not occur under specified

conditions, it is said to be nonspontaneous,
examples:
• A waterfall runs downhill, but never up,
spontaneously.
• A lump of sugar spontaneously dissolves in a
cup of coffee, but dissolved sugar does not
spontaneously reappear in its original form.
• Water freezes spontaneously below 0°C, and
ice melts spontaneously above 0°C (at 1 atm).
 Entropy, S
1. One property common to
spontaneous processes is that
the final state is more
DISORDERED or RANDOM
than the original.
2. Spontaneity is related to
an increase in
randomness.
3. The thermodynamic property
related to randomness is
ENTROPY, S. Reaction of K
with water
The entropy of
liquid water is
greater than
the entropy of
solid water
(ice) at 0˚ C.
 Entropy, S

So (J/K•mol)
H2O(liq) 69.95
H2O(gas)188.8

S (gases) > S (liquids) > S (solids)

 Standard Molar Entropies
Standard entropy is the absolute entropy of a substance at 1 atm and
25°C.
 Entropy Changes for Phase
Changes
For a phase change,
∆S = q/T
where q = heat transferred in
phase change
For H2O (liq) ---> H2O(g)
∆H = q = +40,700 J/mol

q 40,700 J/mol
DS = = = + 109 J/K • mol
T 373.15 K
Entropy and Temperature

S increases
slightly with T

S increases a
large amount
with phase
changes
 Calculating ∆S for a Reaction

∆So =  So (products) -  So(reactants)

ΔS°> 0, the system becomes more disordered
ΔS°< 0, the system becomes less disordered or more ordered

Consider 2 H2(g) + O2(g) ---> 2 H2O(liq)

∆So = 2 So (H2O) - [2 So (H2) + So (O2)]
∆So = 2 mol (69.9 J/K•mol) -
[2 mol (130.7 J/K•mol) +
1 mol (205.3 J/K•mol)]
∆So = -326.9 J/K less disordered
 Gibbs Free Energy

• Gibbs Free Energy can be used to predict

the spontaneity and it ties together the DH
and the DS, the two driving forces of
reactions.
DG= DH-TDS
 Gibbs Free Energy
Energy that can be converted to work.

DG<0 for spontaneous processes.

DG=0 at equilibrium.
 Gibbs Free Energy, G
Two methods of calculating ∆Go (Standard)
a) Determine ∆Horxn and ∆Sorxn and use GIbbs
equation.
∆Go = ∆Ho - T∆So
b)Use tabulated values of free energies of
formation, ∆Gfo.

∆Gorxn =  ∆Gfo (products) -  ∆Gfo(reactants)

Free Energies of Formation

Note that ∆G˚f for an element = 0

 Calculating ∆Gorxn
Combustion of acetylene
C2H2(g) + 5/2 O2(g) --> 2 CO2(g) + H2O(g)
Use enthalpies of formation to calculate
∆Horxn = -1255.5 kJ ΔHf H2O(g) = -241.8 kJ/mol
ΔHf CO2(g) = -393.5 kJ/mol
ΔHf C2H2(g) = 226.7 kJ/mol

Use standard molar entropies to calculate

∆Sorxn = -97.51 J/K ΔS H2O(g) = 188.84 J/mol.K
ΔS CO2(g) = 213.7 J/mol.K
ΔS C2H2(g) = 201 J/mol.K
ΔS O2(g) = 205.1 J/mol.K

∆Gorxn = -1255.5 kJ - (298 K)(-97.51/1000 kJ/K)

= -1226.4420 kJ reaction is spontaneous at low T
 Calculating ∆Gorxn
∆Gorxn =  ∆Gfo (products) -  ∆Gfo (reactants)

Combustion of carbon
C(graphite) + O2(g) --> CO2(g)
∆Gorxn = ∆Gfo(CO2) - [∆Gfo(graph) + ∆Gfo(O2)]
∆Gorxn = -394.4 kJ - [ 0 + 0]
Note that free energy of formation of an element in
its standard state is 0.
∆Gorxn = -394.4 kJ
reaction is spontaneous
 Four possible conditions
ΔH ΔS ΔG Spontaneity Example
Spontaneous at all T 2NO2 = N2 + 2O2
- + -
Spontaneous at low T, N2 + 3H2 = 2NH3
- Or
- - nonspontaneous at high T
+
Non spontaneous at all T 3 O2 = 2 O3
+ - +
Spontaneous at high T, 2HgO = Hg + O2
- Or
+ + nonspontaneous at low T
+
 Thermodynamics and Keq
• In most reactions, the reactants and products are
not in standard states

DG  DG  RT ln Q where R = 8.31 J/K•mol

o

Q is the reaction quotient – similar in form to K

– Pressures for gases
– Concentrations for liquids

N 2 ( g )  3H 2 ( g )  2 NH3 ( g )
2
p
Q
NH 3
3
p p
N2 H 2
Relationship between ΔGº and K

At equilibrium, ΔG = 0, Q=K
ΔG° = -RT ln K

ΔGº Ln K K Comment

Mainly products
<0 >0 >1

Mainly reactants
>0 <0 <1

Even ratio of reactants

=0 =0 1
and products
 Thermodynamics and Keq

∆Gorxn = - RT lnK
Calculate K for the reaction
N2O4 2 NO2 ∆Gorxn = +4.8 kJ
∆Gorxn = +4800 J = - (8.31 J/K)(298 K) ln K
4800 J
ln K = - = -1.9383
(8.31 J/ K)(298 K)
K = 0.1439
When ∆Gorxn > 0, then K < 1 Mainly reactants