CHM 101

(INTRODUCTORY CHEMISTRY I)

THERMOCHEMISTRY (2)
ORDER – DISORDER PHENOMENON
 ENTROPY
Entropy: A thermodynamic function that measures the degree of randomness or
disorder in a system. It is denoted as S. Its unit is J.K−1.mol−1
• Entropy is a state function and an extensive property.
(State function: property whose value doesn’t depend on the path taken to reach
that specific value is known to as state functions or point functions- they depend on
the state of the substance like temperature, pressure or the amount or type of the
substance. An extensive property is a property that depends on the amount of
matter in a sample.)
• During change of state, systems tend to a state of greatest disorder (high entropy)
– Second Law of Thermodynamics

↑entropy = ↑disorder
The greater the randomness, the higher the entropy. As the solid changes through
the liquid to the gaseous state. i.e., gaseous systems show much greater disorder
than liquid systems, which in turn show greater disorder than solid systems.
 To determine the direction of change in
entropy……
Second law of thermodynamics states that all closed system tend to
maximize entropy (Reversing the ever increasing tendency requires the
input of energy)
e.g. Solid → Liquid → Gas.
:
Lump of ice → liquid (heat is absorbed from the surroundings,
disorderliness increases, higher energy)
∆S = Sproduct – Sreactant
When Sproduct < Sreactant , ∆S = -ve
When Sproduct > Sreactant , ∆S = +ve
1. Change of State :
When a substance changes to a state of higher energy, the entropy
increases (∆S = +ve). But if the change is to a state of lower energy,
entropy decreases (∆S = -ve).
e.g. H2O(l) → H2O(g) ∆S = +ve (increase in disorder)
H2O(l) → H2O(s) ∆S = -ve (decrease in disorder)

…..Positive entropy therefore indicates spontaneity of the process

(following this law)
 2. Decomposition or Composition:
When a substance decomposes into 2 or more substances, entropy
increases i.e. ∆S = +ve. But if two or more substances compose into a
single substance, entropy decreases i.e. ∆S = -ve

e.g. CaCO3(s) → CaO(s) +CO2(g) ∆S = +ve (disordered)

N2(g) + 3H2(g) → 2NH3(g) ∆S = -ve(ordered)
2HCl(s) → H2(g) + Cl2(g) ∆S = +ve (disordered)
3. Change in Volume Occupied:
when a gaseous substance decomposes into another gas of smaller volume,
entropy decreases; but entropy increases if the product is of higher volume.
• Example, N O 2 NO
2 4 2

Here, volume changes from 1 vol. in N2O4 to 2 vols. in NO2, therefore,

entropy increases. i.e. ∆S = +ve.
Note in summary:
The entropy change involved when a system changes from an
orderly state to a disorderly state is always positive (∆S = +ve).
From a disorderly state to an orderly state, entropy is always
negative (∆S = -ve).
ENTHALPY
 ENTHALPY
Source: https://www.slideshare.net/mrtangextrahelp/tang-
01b-enthalpy-entropy-and-gibbs-free-energy
Enthalpy (H) is expressed as
H = U + PV
U = internal energy
P = Presssure
V = Volume
• When a process occurs at constant
pressure, the heat flow (q or Q) (either
released or absorbed) for the process is
equal to the change in enthalpy.
i.e ΔH = q
• Enthalpy is a state function which
depends entirely on the state functions
T , P and U .
• The unit of molar enthalpy is J.mol-1.
ENTHALPY CHANGES: Exothermic and endothermic reactions
• Enthalpy is usually expressed as the change in
enthalpy (ΔH ) for a process between initial
and final states

• When a system (reaction) loses heat to the

surrounding, the reaction is exothermic. i.e.
∆H is –ve (∆Hproduct < ∆Hreactant )

• When a system (reaction) absorbs heat from https://cdn1.byjus.com/wp-content/uploads/2016/06/Energy-

the surrounding, the reaction in endothermic
i.e. ∆H = +ve (∆Hproduct > ∆Hreactant ) Level-Diagram-of-an-Endothermic-Reaction-700x410.png
ENTHALPY OF REACTION
• When energy needs to be added
to a material to change
its phase from a liquid to a gas,
that amount of energy is called
the enthalpy (or latent heat) of
vaporization
• Other phase transitions have
similar associated enthalpy
changes, such as the enthalpy (or
latent heat) of fusion for changes
from a solid to a liquid
• Enthalpy of reaction is the enthalpy
charge accompanying a reaction
represented by a balanced chemical
equation.
• For any physical or chemical process
where there is an enthalpy change,
the reverse process will be
accompanied by the reverse enthalpy
change (i.e. change in sign)
e.g.
C(s) + O2(g) →CO2(g) ∆H = -394 kJ mol-1
CO2(g) →C(s) + O2(g) ∆H = +394 kJ mol-1
 ∆H can be related to the number of moles of each
reactant…..
e.g. The phase (or state) of each substance (gas,
liquid or solid) taking part in the reaction must
be specified.
4Cr(s) + 3O2(g) →2Cr2O3(s) ∆H = -2256 kJ mol-1 (i)
C(graphite) + O2(g) → CO2(g) ∆H = -394 kJ mol-1
This should be written as:
3
2Cr(s) + O2(g) → Cr2O3(s) ∆H = -1128 kJ mol -1 (ii)
2 ∆H depends on the state of substances.

e.g.
Note: The stoichiometry coefficient of the
1
reaction in (ii) is a fraction of reaction (i). H2(g) + O2(g) →H2O(l) ∆H = -286 kJ mol-1___(i)
2
Hence, ∆H value changes 1
H2(g) + 2O2(g) →H2O(g) ∆H = -242 kJ mol-1___(ii)
Example 1:
How much heat is evolved when mass given = 500kg = 500 x 103g
500 kg of ammonia is produced 500×103 𝑔
჻ 𝑛𝑁𝐻3 = = 2.94 × 104 mol
according to the following equation? 17𝑔 𝑚𝑜𝑙 −1

N2(g) + 3H2(g) →2NH3(g) From the balanced chemical

equation,
∆H= -91.8 kJ mol-1
2 moles of NH3 gave -91.8 kJ mol-1.
[N = 14.0, H = 1.00g mol-1].
჻ 2.94 × 104 mol of NH3 will give:
Solution: −91.8 kJ mol−1
𝑚𝑎𝑠𝑠 𝑔𝑖𝑣𝑒𝑛 × 2.94 × 104 𝑚𝑜𝑙
No of moles of NH3 =
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑁𝐻3
2𝑚𝑜𝑙

= −1.35 × 106 𝑘𝐽 𝑚𝑜𝑙 −1

molar mass of NH3 = 14 + 3(1.00) = 17 g mol-1
ΔH, o
ΔH reaction and the Standard state
Δ = represents the change in the enthalpy;
O= signifies that the reaction is a standard
enthalpy change,
reaction = denotes that this change is the enthalpy
of reaction
∆Hreaction = ∑n∆Hp – ∑m∆Hr
where:
∑ represents summation
n and m are the coefficients of the substances in
the product(s) and reactant(s) respectively
Hp =enthalpies of the product(s)
Hr = enthalpies of the reactant(s)
The Standard State:
• The standard state of a substance is the pure
substance in a specified state(solid or liquid or gas)at
1 atm pressure.
• Standard conditions are:
- gases at a pressure of 1 atm ( 105 Pa)
- solutions in unit concentration
- substances in their standard state
• The ΔHoreaction is the standard heat of reaction or
standard enthalpy of a reaction, and like ΔH also
measures the enthalpy of a reaction. However,
ΔHoreaction takes place under "standard" conditions,
meaning that the reaction takes place at 25o C and 1
atm.
• The benefit of a measuring ΔH under standard
conditions lies in the ability to relate one value of
ΔHo to another, since they occur under the same
conditions.
Enthalpy Change Accompanying a Change in State
A change in state involves a change in enthalpy
1. Enthalpy of fusion or enthalpy of melting
(ΔH𝑓𝑢𝑠𝑖𝑜𝑛 )
- the enthalpy change when one mole of a
substance melts.
e.g For example, for one mole of ice the enthalpy is given as:
ΔHfusion = 6.01 kJ at 273.15 K
2. Enthalpy of freezing (ΔH𝑓𝑟𝑒𝑒𝑧𝑖𝑛𝑔 )
- Enthalpy change when one mole of a substance
freezes.
ΔHfreezing = - ΔHfusion
3. Enthalpy of vaporization (ΔHvap )
-heat required to vaporize one mole of a
substance.
ΔHvap = ΔHvapor - ΔHliquid
e.g for one mole of water, ΔHvap = 44.0 kJ at 298 K
4. Enthalpy of condensation (ΔHcondensation )
ΔHcondensation = -ΔHvap
5. Enthalpy of sublimation
ΔHsublimation= ΔHfussion+ Δhvap
Specific temperatures the change takes place are
stated in all enthalpies of phase changes
Relationship between Temperature and Heat
• When the temperature
increases, the amount of
molecular interactions also
increases.
• As the number of
interactions increase, the
internal energy of the system
rises.
• if the internal energy (U)
increases then, the ΔH
increases as temperature
rises. (since H = U +PV)
Specific heat capacity ( c ) is the heat required
to raise the temperature of a unit mass of
substance by 1o C (unit is J K-1 g-1 or J oC-1g-1)
ℎ𝑒𝑎𝑡 𝑐𝑎𝑝𝑎𝑐𝑖𝑡𝑦
Specific heat capacity, c =
𝑚𝑎𝑠𝑠 (𝑚)
(1)
𝑄𝑢𝑎𝑛𝑡𝑖𝑡𝑦 𝑜𝑓 ℎ𝑒𝑎𝑡 (𝑄)
𝐻𝑒𝑎𝑡 𝑐𝑎𝑝𝑎𝑐𝑖𝑡𝑦 = (2)
𝑅𝑖𝑠𝑒 𝑖𝑛 𝑡𝑒𝑚𝑝 (∆𝑇)
Combining equations (1) and (2) we obtain,
𝑄 = 𝑚𝑐∆𝑇 (3)
Examples
(1) Water has specific heat 4.18 J K-1g-1. 100 g of water rise in temperature by
2.0 K. Calculate the heat quantity absorbed by water.
Solution: q = mc∆T
= 100g x 4.18 J K-1g-1 x 2.0 K
= 9.36 J
(2) 293.7 J of heat is removed from 5g of Aluminum causing the temperature
to drop from 85⁰C to 19⁰C. What is the specific heat capacity of Aluminum?
Solution: q = mc∆T
-293.7 J = (5g) (c)(292-358 K)
-293.7 J = -330 c (g. K)
c = 0.89 J K-1 g-1
3. A 50g of an unknown material at 200⁰C was added to 100g of water at 25⁰C. The
final temp of the mixture was 41.8⁰C. What is the specific heat capacity of the
unknown material? (Water has the sp. heat capacity of 4.18 J oC-1g-1)
𝑚𝑒𝑡𝑎𝑙
41.8⁰C (q = -ve)
200⁰𝐶

𝐻2 𝑂
41.8⁰C (q = +ve).
25⁰𝐶
But, Qm = QH20
჻ - Qm = QH20
- mc∆T = - mc∆T
-mc (Tf – Ti) = -mc (Tf – Ti).
-50(c) (25 – 200 oC) = 100 (4.184) (41.8 – 25⁰C)
7910(c) = 7029.12
c = 0.8895 J.
specific heat capacity of the material is 0.8895 J oC-1g-1