Chap 1 Thermodynamic (150318)
Chap 1 Thermodynamic (150318)
Chap 1 Thermodynamic (150318)
CHAPTER 1
THERMODYNAMIC
Mardhiah Ismail
Outline
• 1.1Types of system
• 1.2 First law of thermodynamic
o 1.2.1 internal energy
o 1.2.2 Specific heat and heat capacity
o 1.2.3 Concept of enthalpy
o 1.2.4 Effect of temperature on enthalpy
o 1.2.5 Reversible and non reversible process
o 1.2.6 Types of thermal process
• System can
o Absorb/release heat
o can do work / can have work done for it
• Types :
o Open system : can exchange energy and mass
o Closed system : can exchange energy not mass
o Isolated system : can not exchange energy and mass
Three types of systems
Thermodynamic
• What is Thermodynamics?
o Study of the energy changes that accompany physical
and chemical changes
ΔE= Ef –Ei
The First Law
Internal Energy
• The change in the internal energy of a system is
equal to :
o the sum of the heat gained or lost by the system
o the work done by or on the system.
ΔE= q+ w
The First Law
Internal Energy
• The internal energy and temperature of a system
decrease (E< 0) when the system either loses heat
or does work on its surroundings.
Answer:
Compression is work done on the gas, so the sign for w is positive, w =
462 J, whereas q is negative because heat is transferred from the
system to the surrounding, q = -128 J.
∆E = q + w
= -128 J + 462 J
= 334 J
Example 1.2
When petrol burns in an engine, CO2 and H2O are formed and cause
the volume to expand by pushing the piston upward. The work done by
the system (pushing the piston) is 415 J and the system lost 350 J of
heat to surrounding, calculate the change in energy. DE in kJ
DE sys= q + w
DE = -350 + (-415) = -765 J
= -0.765 kJ
1.2.2 Specific Heat and Heat Capacity
Specific heat (s) : amount of heat required to raise its temperature of 1g of
substance by 1oC
q = m.s. Dt
q = C. Dt
Dt = tfinal - tinitial
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How much heat is given off when an 869 g iron bar cools
from 94oC to 5oC?
s of Fe = 0.444 J/goC
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1.2.3 Enthalpy, H
∆H = ∆E + ∆nRT
• ∆ n= moles of gas(product) –moles of gas(reactant)
• The heat supplied at constant pressure is equal
to the change in enthalpy, H.
H = E + PV
DH = DE + DnRT
A Comparison of DH and DE
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The difference between DE and DH is usually small, so 2
values are almost equal and in many cases DE = DH
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• The relationship between the change in the internal
energy of the system during a chemical reaction
and the enthalpy of reaction can be summarized
as follows:
Dn = 2mol-3 mol
= -1 mol
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Example 1.4: The heat of combustion of methane, CH4 at
constant volume is -885.2 kJ/mol. What is the enthalpy of
the reaction at 250C?
Dn = 1mol-3 mol
= -2 mol
DH = DE + DnRT
= -885.2 x 10-3 J + (-2 mol)(8.314J/K.mol)(298K)
= -890155 J = -890.2 kJ
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1.2.5 Reversible and Irreversible Processes
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• Irreversible processes cannot be undone by exactly reversing the
change to the system.
• Process which both the system and surroundings cannot return to their
original conditions.
For an ideal gas, this process implies that volume and pressure of
product are constant
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Work and heat exchange
in the reversible isothermal
compression process
Integrate:
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Calculation of internal energy, ∆E
H = E + PV
So, ∆H= ∆ (E + PV)
= ∆E + ∆PV
= ∆E + ∆nRT
Calculation of q and w
Solution:
Since isothermal process ⟶ ∆E and ∆H are zero
Work can be calculated using
∆U = ∆E 37
Adiabatic Process
There is no transfer of heat to or from the system, so
q = 0, but ∆T ≠ 0
So, ∆E = nCv ∆T = P ∆V
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Pressure-Volume Work
• Reactions also do work on their surroundings when the
volume of the system expands during the course of the
reaction.
• P constant ⟶V change
• V constant ⟶ P change
Pressure-Volume Work
Isobaric-Constant pressure, Cp
Most chemical reaction are conducted at
constant pressure
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Isobaric-Constant pressure, Cp
When gas is heated at constant P it will caused expansion
of gas, ↑V take place,
w = -PDV
W= -P (Vb-Va)
**units for W= N.m or L.atm
Most chemical reaction are conducted at constant
pressure rather constant volume
∆E = qp-P∆V
rearrange
qp = ∆E + P∆V
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Isometric/Constant Volume,Cv
No external work done when gas is heated at constant
V⟶no PV work is done because no expansion on
system⟶W=0
∆E sys = q + w = q + 0 = qv
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Example 1.6: A sample of nitrogen gas expands in volume from
1.6 L to 5.4 L at constant temperature. What is the work done in
joules if the gas expands (a) against a vacuum and (b) against
a constant pressure of 3.7 atm? ( 1 L.atm = 101.3 Joule)
w = -P DV
w = -P (Vb – Va)
(a) DV = 5.4 L – 1.6 L = 3.8 L P = 0 atm
W = -0 atm x 3.8 L = 0 L•atm = 0 joules
W= -P (Vb – Va)
= - 3.5 atm ( 13.5 L – 10.0 L)
= -12.25 L.atm
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Example 1.7
Example 1.8
1.3 The Second Law (spontaneity)
• 2nd law of
thermodynamic states
that the entropy of the
universe increases in a
spontaneous process and
remains unchanged in
equilibrium process.
• Spontaneous processes are
those that can proceed
without any outside
intervention
• The gas in vessel B will
spontaneously effuse into
vessel A
The Second Law (spontaneity)
• Processes that are
spontaneous in one
direction are non-
spontaneous in the
reverse direction.
The Second Law(spontaneity)
Spontaneous
Nonspontaneous
The Second Law(spontaneity)
The Second Law (spontaneity)
• Spontaneous process
o favoured by decrease in enthalpy (∆H<0)
o favoured by increase in entropy (∆S>0)
3. NaCl(aq) → NaCl(s)
Entropy Changes in the Universe
• The entropy of universe is composed of the system and
the surroundings.
• Therefore,
Standard entropies
tend to increase with
increasing molar mass.
Entropy Changes in the System
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Entropy Changes in the System
When gases are produced (or consumed)
• If a reaction produces more gas molecules than it
consumes, DS0 > 0.
• If the total number of gas molecules diminishes, DS0 < 0.
• If there is no net change in the total number of gas
molecules, then DS0 may be positive or negative BUT DS0
will be a small number.
What is the sign of the entropy change for the following
reaction? 2Zn (s) + O2 (g) 2ZnO (s)
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Gibbs Free Energy
DG = DHsys -TDSsys
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Gibbs Free Energy
The standard free-energy of reaction (DG0 ) is the
rxn free-
DG = DH - TDS
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Effect of temperature on spontaneity
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Example 1.9:
Given ΔH and ΔS for decomposition of potassium chlorate are
-144 kJ and -36.8 J/K respectively. Calculate ΔG for the
reaction at 250C. Is the reaction spontaneous?
4KClO3 3KClO4 + KCl
Solution:
ΔG= ΔH – TΔS
= - 144 000 J – [(298K)(-36.8 J/K)]
=-133034 J
=-133kJ
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Example 1.20:
Hydrogen reduces iron (III) oxide to iron metal.
Fe2O3 + 3H2 Fe + 3H2O
Enthalpy change for the reaction is 98.8 kJ and the entropy change is 141.5 J/K.
a) Is the reaction spontaneous at 40OC
b) What is the temperature for the reaction to be spontaneous?
Solution:
a) ΔG= ΔH – TΔS
= - 98.8 x103 J – [(298K)(141.5 J/K)]
= 56.6 x103 J
= 56.6 kJ
T = ΔH
ΔS
= 98.8 kJ
0.1415 kJ/ K
=698 K
=425OC
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Temperature and Spontaneity
CaCO3 (s) CaO (s) + CO2 (g)
Equilibrium Pressure of CO2
DH0 = 177.8 kJ/mol
DS0 = 160.5 J/K·mol
at 835 oC
DG0 = 177.8 x 103 – 1108 (160.5) = 0 kJ/mol
Forward reaction is spontaneous when T > 835 oC
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