6-th lesson

Thermodynamics

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Thermochemistry study the energy effect of
chemical reaction

Chemical reaction energy changes are utilized

to :
 Calculate the heat balance of industrial
processes;
 Determine the energy of bonds;
 Establish the direction of processes.

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Classification of chemical systems
Chemical system –
a number of substances and
Interactions proceeding in
a limited volume

OPEN CLOZE ISOLATE

Δm ≠ 0 Δm = 0 Δm = 0
ΔQ ≠ 0 ΔQ ≠ 0 ΔQ = 0

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 Any
chemical system
is characterized by

Parameters Functions of state

Absolute values can’t be
can be measured
measured

Mass m,
Internal energy E,
Temperature T,
Enthalpy H,
Pressure P,
Entropy S,
Amount of substance n,
Gibbs free energy G
Concentration c

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 Types of chemical reactions

Chemical
reaction

Exothermic Q>0 (ΔHm<0) Endothermic Q<0 (ΔHm>0)

Heat is liberated Heat is absorbed from

into the surroundings the surroundings

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 Types of chemical reactions

Chemical
reaction

Isobaric Δp=0 Isochoric ΔV=0

at constant pressure at constant volume

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 First Law of Thermodynamics
 The energy cannot be created nor destroyed.
 Therefore, the total energy of the universe is a
constant.
 Energy can, however, be converted from one form to
another or transferred from a system to the
surroundings:
Q = ΔU + A,
where Q – an amount of heat;
ΔU – changes in internal energy;
A – a work resisting external forces:
A = PΔV .
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 Enthalpy – heat content

 If a system is exchanged with surroundings by

heat its’ internal energy and enthalpy are
changed:
 Q > 0 (heat is liberated) ΔU < 0, ΔH < 0;
 Q < 0 (heat is absorbed) ΔU > 0, ΔH > 0.
 The value of ΔH is corresponding to the amount
of the heat Q which is absorbed or evolved in
any chemical reaction:
Q = – ΔH

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 Standard Enthalpy of Formation

 The standard enthalpy of formation ΔHf

is the enthalpy change when 1 mol of a
pure substance is formed from its elements.
 Each element must be in the physical and
chemical form which is most stable at
normal atmospheric pressure (101325 Pa
or 1 atm) and a specified temperature
(usually 298 K or 25 °C).

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 Standard Enthalpy of Formation

 If ΔHf[H2O(l)] = –285.8 kJ· mol–1 the

thermochemical equation is:
H2(g) + ½O2(g) → H2O(l) + 285.8
ΔHm = –285.8 kJ·mol–1
 The standard enthalpy of formation for a
simple substance in its most stable state
must be zero.

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 Some Standard Enthalpies of Formation at 25°C.
Compound ΔHf/kJ·mol–1 Compound ΔHf/kJ·mol– Compound ΔHf/kJ·mol–
1 1

AgCl(s) –127.068 CaO(s) –635.09 KCl(s) –436.747

AgN3(s) +620.6 CaCO3(s) –1206.92 KBr(s) –393.798
Ag2O(s) –31.0 CuO(s) –157.3 MgO(s) –601.7
Al2O3(s) –1675.7 Fe2O3(s) –824.2 NH3(g) –46.11
Br2(l) 0.0 HBr(g) –36.4 NO(g) +90.25
Br2(g) +30.907 HCl(g) –92.307 NO2(g) +33.18
C(s), graphite 0.0 HI(g) +26.48 N2O4(g) +9.16
C(s), diamond +1.895 H2O(g) –241.818 NF3(g) –124.7
CH4(g) –74.81 H2O(l) –285.8 NaBr(s) –361.062
CO(g) –110.525 H2O2(l) –187.78 NaCl(s) –411.153
CO2(g) –393.509 H2S(g) –20.63 O3(g) +142.7
C2H2(g) +226.73 HgO(s) –90.83 SO2(g) –296.83
C2H4(g) +52.26 I2(s) 0.0 SO3(g) –395.72
C2H6(g) –84.68 I2(g) +62.438 ZnO(s) –348.28
C6H6(l) +49.03
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 To calculate ΔH we add all the ΔHf values for the
products, multiplying each by the appropriate
coefficient.
 Than we add all the ΔHf values for the reactants
again multiplying by appropriate coefficients.
This can be summarized by the equation

ΔH = ∑ iΔHf (products) – ∑ jΔHf (reactants)

the symbol Σ means “the sum of”,

i,j – coefficients in the teaction.

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 Spontaneous Processes

 Spontaneous processes
are those that can
proceed without any
outside intervention.
 The gas in vessel B will
spontaneously effuse into
vessel A, but once the gas
is in both vessels, it will
not spontaneously

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Spontaneous Processes

Processes that are

spontaneous in one
direction are
nonspontaneous in the
reverse direction.

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 Spontaneous Processes
 Processes that are spontaneous at one
temperature may be nonspontaneous at other
temperatures.
 Above 0C it is spontaneous for ice to melt.
 Below 0C the reverse process is spontaneous.

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 Entropy (S) is a state function

 Entropy can be thought of as a measure of

the randomness of a system.
 It is related to the various modes of motion in
molecules.
 Molecules exhibit several types of motion:
 Translational: movement of the entire molecule
from one place to another.
 Vibrational: periodic motion of atoms within a
molecule.
 Rotational: rotation of the molecule on about an
axis or rotation about  bonds.

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Entropy on the Molecular Scale

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 Entropy on the Molecular Scale
 Each thermodynamic state has a specific number of
microstates, W, associated with it.
 Entropy is
S = k lnW
where k is the Boltzmann constant, 1.381023 J/K.

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 Second Law of Thermodynamics

The entropy of the universe increases

for spontaneous processes:

ΔS > 0

Each system is tended to a randomization

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 Entropy on the Molecular Scale

Implications:

• more particles
-> more states -> more entropy
• higher T
-> more energy states -> more entropy
• less structure (gas vs solid)
-> more states -> more entropy

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 Entropy on the Molecular Scale

 The number of microstates and, therefore,

the entropy tends to increase with increases
in
 Temperature.
 Volume (gases).
 The number of independently moving
molecules.

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 Entropy and Physical States

 Entropy increases
with the freedom of
motion of
molecules.
 Therefore,
S(g) > S(l) > S(s)

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 Entropy Changes

 In general, entropy
increases when
 Gases are formed from
liquids and solids.
 Liquids or solutions are
formed from solids.
 The number of gas
molecules increases.
 The number of moles
increases.

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 Third Law of Thermodynamics
The entropy of a pure crystalline
substance at absolute zero is 0.

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25
Standard Entropies

 These are molar

entropy values of
substances in their
standard states.
 Standard entropies
tend to increase with
increasing molar mass.

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 Standard Entropies

Larger and more complex molecules have

greater entropies.

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 Entropy Changes

Entropy changes for a reaction can be calculated

the same way we used for H:

ΔS = ∑ iS0 (products) – ∑ jS0 (reactants)

S° for each component is found in a table.

Note for pure elements:

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 Standard Free Energy Changes

Standard free energies of formation, Gf are

analogous to standard enthalpies of
formation, Hf.

ΔG = ∑ iΔGf° (products) – ∑ jΔGf°

(reactants)

G can be looked up in tables,

or
calculated from S° and H.

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 Free Energy Changes

Very key equation:

This equation shows how G changes with

temperature.
(We assume S° and H° are independent of T.)

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Gibbs Free Energy

• If  G is negative,
the forward
reaction is
spontaneous.
• If ΔG is 0, the
system is at
equilibrium.
• If G is positive,
the reaction is
spontaneous in the
reverse direction.

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 Free Energy and Temperature

 There are two parts to the free energy

equation:
 H – the enthalpy term
 TS – the entropy term

 The temperature dependence of free energy

comes from the entropy term.

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 Free Energy and Temperature

By knowing the sign (+ or -) of S and H,

we can get the sign of G and determine if a
reaction is spontaneous.

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 Free Energy and Equilibrium

Remember from above:

If ΔG is 0, the system is at equilibrium.

So Δ G must be related to the equilibrium

constant, K.
The standard free energy, ΔG°, is directly
linked to Keq by:

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