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Chemical
Thermodynamics
LESSON OUTCOMES
At the end of this lecture, students should be
able to:
1. Recognize and use thermodynamic terms:
system, surrounding, heat, work, internal
energy, Gibbs Free energy, enthalpy and
entropy
2. Describe the first law of thermodynamics
3. Calculate the change in internal energy
2
Thermochemistry
Chapter Outline
Forms of Energy and Their Interconversion
Enthalpy: Heats of Reaction and Chemical
Change
Calorimetry: Laboratory Measurement of Heats
of Reaction
Stoichiometry of Thermochemical Equations
Hess’s Law of Heat Summation
Standard Heats of Reaction
All changes in matter - accompany by changes in
the energy/heat content of the matter.
e.g. 1. Snow melts - energy is absorbed
2. H2O vapor condenses to rain - energy is
release
7
The system and Its Surroundings
and surroundings
Work, w
energy transferred when an object is moved by a force
Calculating E in J:
q = -325 J, w = -451 J,
E =q+w
= -325 J + (-451J) = -776 J
State Functions and the Path Independence of
the Energy Change
System’s internal energy, E - state of function
property determined by the current state of the system
not dependent on the path the system took to reach the
state
Changes in state function (such as E, P, V) depend
only on the initial and final states of the system
For a given change, E (sum of q and w) is constant, even
though the specific values of q and w can vary
Heat, q and work, w are not state function their values
depend on the path the system takes in undergoing the
energy change
Note: Symbols for state functions (such as E,P,V) are
capitalized
Enthalphy: Heats of Reaction and Chemical
Change
The Meaning of Enthalphy
Heat & work must be measured to determine E
Two most important type of chemical work
(i) electric work - work done by moving charged
particles
(ii) PV work - work done by expanding gas
PV work
Quantity PV work = multiple the external pressure (P) by
the change in volume of the gas (V, or Vfinal - Vinitial)
w = -PV
e.g. In an open flask, a gas done work by pushing back
the atmosphere. work done on the surroundings is -ve
because the system loses energy
w = -PV (2)
At constant pressure, q = qp
E = qp - PV
qp = E + PV (4)
where E + PV = H
Comparing E and H
For many reactions, H is equal / very close to E. Three
cases
V 0, PV 0, H E
(ii) Reactions in which the amount (mol) of gas does not
change. Total amount of gaseous reactants = total
amount of gaseous products
e.g. N2(g) + O2(g) 2NO(g), V = 0, PV = 0, H E
Solution
(a) Heat is a product (on the right), so H 0 and the
reaction is exothermic
(b) Heat is a reactant (on the left), so H 0 and the
reaction is endothermic
Some Important Types of Enthalpy Change
(i)Heat of combustion (Hcomb): when 1 mole of substance
reacts with O2 in a combustion reaction
e.g. C4H10(l) + 13/2 O2(g) 4CO2(g) + 5H2O, H = Hcomb
Solution
Constant-Pressure Calorimetry
A coffee/styroform-cup calorimeter
Use to measure the heat (qp) of many processes that
are open to the laboratory atmosphere
Common use - to determine the specific heat capacity
of a solid (does not react/dissolve in water)
Process:
solid (system) is
weighed, heated
to some known
temperature,
added to a sample
of water
(surroundings) of
known
temperature &
mass in the
calorimeter
Continual stirring which distribute the released heat
Final water temperature (final temperature of the solid)
is measured
Solution
Plan -summarize the information given.
Calculating csolid
J
4.184 x 50.00 g x 3.93K
cH O x massH O x ΔTH O gK
c solid 2 2 2
masssolid x ΔTsolid 25.64 g x (71.51K)
J
0.387
gK
Constant-Volume Calorimetry
Common type: bomb
calorimeter
Use to measure very
precisely the heat released
in combustion reaction
Knowing mass of the
sample and the heat
capacity of the calorimeter,
the measured T is used to
calculate the heat released
Example
Thermochemical equations
a balanced equation that states the heat of reaction ( Hrxn)
factor
• Add eq. 1 to the halved eq. 2, cancel terms that appear on both
sides:
e.g.
C(graphite) + 2H2O(g) CH4(g) H0f = -74.9 kJ
Example
Write balanced equations for the formation of 1 mole of the
following compounds from their elements in their standard states
and include H0f (To obtain values, refer to Table 6.5 - page 244,
Chemistry: the molecular nature of matter and change, 2nd Edition,
Silberberg)
(i) Silver chloride, AgCl, a solid at standard conditions
(ii) Calcium carbonate, CaCO3, a solid at standard conditions
(iii) Hydrogen cyanide, HCN, a gas at standard conditions
Solution
(i) Ag(s) + 1/2 Cl2(g) AgCl(s) H0f = -127.0 kJ
(ii) Ca(s) + C(graphite) + 3/2 O2(g) CaCO3 H0f = -1206.9 kJ
(iii) 1/2 H2(g) + C(graphite) + 1/2 N2(g) HCN H0f = 135 kJ
Determining H0rxn from H0f values of
Reactants and Products
Solution
H0rxn = mH0f (products) - mH0f (reactants)
= {4H0f [NO(g)] + 6H0f [H2O(g)]} - {4H0f [NH3(g)] +
5H0f [O2(g)]}
= [4 mol (90. 3 kJ/mol) + 6 mol (-241.8 kJ/mol)] –
[4 mol (-45.9 kJ/mol) + 5 mol (0 kJ/mol)]
= 361 kJ - 1451 kJ + 184 kJ - 0 kJ = -906 kJ
Thermodynamics - Chapter Outline
Spontaneous Processes
Entropy and the Second Law of Thermodynamics
The Molecular Interpretation of Entropy
Calculation of Entropy Changes
Gibbs Free Energy
Free Energy and Temperature
Free Energy and the Equilibrium Constant
Chemical Thermodynamics
Area of chemistry that explores energy relationship
Limitations of First Law Thermodynamics
only tells the amount of heat released/work done by the
system & the amount of heat gained/work done on the
system
sign of H - not enough to predict whether the reaction
will proceed
H - not the only factor governs reactants or
products favoured
Reactants or products favoured In addition to H,
change in randomness or disorder in chemical reaction is
considered
New aspect in discussion of thermodynamics
spontaneous process
related to disorder in chemical reaction
Spontaneous Process
Spontaneous process: Chemical or physical change
occurs by itself
requires no continuing outside agency / occurs without
any outside intervention
A rock at the top of a hill
Entropy change, S
S = Sfinal – Sinitial
Solution
S0 = 2S0(NH3) - [S0(N2) + 3S0(H2)]
Substituting the appropriate S0 values
J J J
ΔS 2 mol 1925 1 mol 191.5 3 mol 130.6
mol K mol K mol K
J
- 198.3
K
Example
Choose the substance that has greater entropy in each pair,
and explain your choice:
(a) 1 mol of NaCl(s) or 1 mol of HCl(g) at 250C
(b) 2 mol of HCl(g) or 1 mol of HCl(g) at 250C
(c) 1 mol of N2(s) at 24 K or 1 mol of N2(g) at 298 K
Second Law of Thermodynamics
Second Law of Thermodynamics: total energy of a system
and its surroundings always increases for a spontaneous
process
Note: the difference between the entropy & energy
energy - cannot be created or destroyed during chemical
change
entropy-created during a spontaneous or natural process
q
ΔS equilibrium process, (Eq.1)
T
Examples of phase changes under equilibrium:
vaporization of a liquid, fusion of a solid
Eq.1 can be used to obtain the entropy change for a phase
change
e.g. Consider the melting of ice, Hfus 6.0 kJ (1 mol of ice)
heat absorbed = heat of fusion, Hfus
q
ΔS =
T
entropy change , Δ Hf us
Δ S=
T
ΔH - TΔS 0 (-ve)
Solution
o
o
(a)ΔG 2 mol ΔGf NH3 1 mol ΔGf N2 3 mol ΔGf H2
o o
kJ kJ kJ
2 mol - 16.66 1 mol 0 3 mol 0
mol mol mol
- 33.32 kJ
equilibriu m constant , K
P Q
p q
A a Bb
Q is calculated by substituting reactant and product
concentrations in the equilibrium-constant expression
Under standard conditions: [reactants] & [products] = 1
Q = 1, ln Q = 0, G = G0
At equilibrium: G = 0, Q = K
G = G0 + RT ln Q
0 = G0 + RT ln K
G0 = -RT ln K
ΔGo
K exp
RT
The End