THERMODYNAMICS.

Elements of Physical Chemistry. By P. Atkins

Concerned with the study of

transformation of energy:
Heat  work
 CONSERVATION OF ENERGY – states that:

⚫ Energy can neither be created nor destroyed in chemical

reactions. It can only be converted from one form to the other.

⚫ UNIVERSE
➢ System – part of world have special interest in…
➢ Surroundings – where we make our observations
 Example:

↔ matter
↔ energy ↔ energy not matter matter ×
×
→ →
Energy

Open system Closed system Isolated system

⚫ If system is thermally isolated called Adiabatic system eg: water
in vacuum flask.
 WORK and HEAT

⚫ Work – transfer of energy to change height of the weight in

surrounding eg: work to run a piston by a gas.

⚫ Heat – transfer of energy is a result of temperature difference

between system and surrounding eg:

HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l) - heat given off.

If heat released to surroundings – exothermic.

If heat absorbed by surroundings – endothermic.
Example: Gasoline, 2, 2, 4 trimethylpentane

CH3C(CH3)2CH2CH(CH3)CH3 + 25/2 O2 → 8CO2(g) +H2O(l)

5401 kJ of heat is released (exothermic)

Where does heat come from?

From internal energy, U of gasoline. Can represent chemical reaction:

Uinitial = Ufinal + energy that leaves system (exothermic)

Or
Ui = Uf – energy that enters system (endothermic)
Hence, FIRST LAW of THERMODYNAMICS (applied to a closed
system)

⚫ The change in internal energy of a closed system is the energy

that enters or leaves the system through boundaries as heat or
work. i.e.
⚫ ∆U = q +w
➢ ∆U = Uf – Ui
➢ q – heat applied to system
➢ W – work done on system
➢ When energy leaves the system, ∆U = -ve i.e. decrease internal
energy
⚫ When energy enter the system, ∆U = +ve i.e. added to internal
energy
 Different types of energies:

1. Kinetic energy = ½ mv2 (chemical reaction) kinetic energy

(KE)  k T (thermal energy) where k = Boltzmann constant

2. Potential energy (PE) = mgh – energy stored in bonds

Now, U = KE + PE
3. Work (W)
w = force × distance moved in direction of force
i.e. w = mg × h = kg × m s-2 × m = kg m2 s-2
(m) (g) (h)

1 kg m2 s-2 = 1 Joule

- Consider work – work against an opposing force, eg: external

pressure, pex. Consider a piston
Piston

Pex pex

pressure (P)

A = area of piston
h is distance moved
 w = distance × opposing force
w = h × (pex × A) = pex × hA

Work done on system = pex × ∆V

∆V – change in volume (Vf – Vi)

 Work done by system = -pex × ∆V

Since U is decreased
Example:

C3H8(g) + 5 O2(g) → 3CO2(g) + 4H2O(l) at 298 K  1 atm

(1 atm = 101325 Pa), -2220 kJ = q

What is the work done by the system?

For an ideal gas;
pV = nRT (p = pex)
n – no. of moles
R – gas constant
T = temperature
V – volume
p = pressure
  V= nRT/p or Vi = niRT/pex

6 moles of gas:
Vi = (6 × 8.314 × 298)/ 101325 = 0.1467 m3

3 moles of gas:
Vf = (3 × 8.314 × 298)/ 101325 = 0.0734 m3

work done = -pex × (Vf – Vi)

= -101325 (0.0734 – 0.1467) = +7432 J
NB: work done = - pex (nfRT/pex – niRT/pex)

= (nf – ni) RT

Work done = -∆ngasRT

i.e. work done = - (3 – 6) × 8.314 × 298 = + 7432.7 J

Can also calculate ∆U

∆U = q +w q = - 2220 kJ
w = 7432.7 J = 7.43 kJ

 ∆U = - 2220 + 7.43 = - 2212.6 kJ

NB:
qp  ∆U why?

Only equal if no work is done i.e. ∆V = 0

i.e. qv = ∆U
Example: energy diagram

C3H8 + 5 O2 (Ui)
U
reaction path

3CO2 + 4H2O(l) (Uf)

progress of reaction
Since work done by system = pex∆V

System at equilibrium when pex = pint (mechanical equilibrium)

Change either pressure to get reversible work i.e.

pex > pint or pint > pex at constant temperature by an infinitesimal

change in either parameter
⚫ For an infinitesimal change in volume, dV
⚫ Work done on system = pdV

For ideal gas, pV = nRT

p = nRT/ V
Vf

 work = p  dV = nRT  dV/ V

Vf

Vi
Vi

= nRT ln (Vf/Vi) because dx/x = ln x

⚫ Work done by system= -nRT ln(Vf/Vi)
 Enthalpy, H

⚫ Most reactions take place in an open vessel at constant

pressure, pex. Volume can change during the reaction
i.e. V  0 (expansion work).

Definition: H = qp i.e. heat supplied to the system at

constant pressure.
Properties of enthalpy

⚫ Enthalpy is the sum of internal energy and the product of pV of

that substance.

i.e H = U + pV (p = pex)

⚫ Some properties of H
 Hi = Ui + pVi
Hf = Uf + pVf

Hf – Hi = Uf – Ui +p(Vf – Vi)

or
H = U + p V
Since work done = - pex V

H = (- pex V + q) +p V
(pex= p)

 H = ( -p V + q) + p V = q

⚫  H = qp
suppose p and V are not constant?

• H = U + ( pV) expands to:

• H = U + pi V + Vi P + (P) (V)

• i.e. H under all conditions.

• When p = 0 get back

H = U + pi V  U + p V
• When V = 0:
H = U + Vi p
 Enthalpy is a state function.

path 1
B
longitude

path 2

lattitude

- does not depend on the path taken

NB: work and heat depend on the path taken and are written as
lower case w and q. Hence, w and q are path functions. The
state functions are written with upper case.

eg: U, H, T and p (IUPAC convention).

 Standard States

⚫ By IUPAC conventions as the pure form of the substance at 1 bar

pressure (1 bar = 100,000 Pa).

What about temperature?

⚫ By convention define temperature as 298 K but could be at any
temperature.
Example:

C3H8(g) + 5 O2(g) → 3CO2(g) + 4H2O(l)

at 1 bar pressure, qp = - 2220 kJmol-1.

⚫ Since substances are in the pure form then can write

H = - 2220 kJ mol-1 at 298 K

 represents the standard state.

 H2(g) → H(g) + H(g), H diss = +436kJmol-1

H2O(l) → H2O(g), H vap = +44.0 kJmol-1

Calculate U for the following reaction:

CH4(l) + 2 O2(g) → CO2(g) + 2H2O(l), H = - 881.1kJmol-1

H = U + (pV)
= U + pi V + Vi p + p V

NB: p = 1 bar, i.e. p = 0

 H = U + pi V

Since -pi V = - nRT,

U = H - nRT
calculation

 U = - 881.1 – ((1 – 2)(8.314)  298)/ 1000

= - 881.1 – (-1)(8.314)(0.298) = - 2182.99 kJ mol-1
 STANDARD ENTHALPY OF FORMATION, Hf

⚫ Defined as standard enthalpy of reaction when substance is formed

from its elements in their reference state.

⚫ Reference state is the most stable form of element at 1 bar

atmosphere at a given temperature eg.
At 298 K Carbon = Cgraphite
Hydrogen = H2(g)
Mercury = Hg(l)
Oxygen = O2(g)
Nitrogen = N2(g)
 NB: Hf of element = 0 in reference state

➢ Can apply these to thermochemical calculations

eg. Can compare thermodynamic stability of substances in
their standard state.

➢ From tables of Hf can calculate H f rxn for any reaction.

Eg. C3H8 (g) + 5O2(g) → 3CO2(g) + 4H2O(l)

⚫ Calculate Hrxn given that:

Hf of C3H8(g) = - 103.9 kJ mol-1
Hf of O2(g) = 0 (reference state)
Hf of CO2(g) = - 393.5 kJ mol-1
Hf of H2O(l) = - 285.8 kJ mol-1

Hrxn = n H (products)- n H(reactants)

 Hf(products) = 3  (- 393.5) + 4  (- 285.8)
= - 1180.5 -1143.2 = - 2323.7 kJ mol-1

Hf(reactants) = - 103.9 + 5  0 = - 103.9 kJ mol-1

Hrxn = - 2323.7 – (- 103.9) = - 2219.8 kJ mol-1

= - 2220 kJ mol-1
⚫ Answer same as before. Eq. is valid.
⚫ Suppose: solid → gas (sublimation)
⚫ Process is: solid → liquid → gas
⚫ Hsub = Hmelt + Hvap

⚫ Ie. H ( indirect route) = . H ( direct route)

Hess’ Law

⚫ - the standard enthalpy of a reaction is the sum of the standard

enthalpies of the reaction into which the overall reaction may be
divided. Eg.
⚫ C (g) + ½ O2(g) → CO (g) , Hcomb =? at 298K
 – From thermochemical data:
⚫ C (g) +O2 (g) → CO 2(g) Hcomb =-393.5 kJmol-
1…………………………….(1)

⚫ CO (g) +1/2 O2 (g) →CO 2(g), Hcomb = -283.0 kJ mol-

1……………………. (2)
⚫ Subtract 2 from 1 to give:
⚫ C (g) + O2 (g) – CO (g) – 1/2 O2 (g) → CO2 (g) – CO2 (g)
⚫  C (g) + ½ O 2 (g) → CO (g) , Hcomb= -393.5 –
⚫ (-283.0) = - 110.5 kJ mol-1
Bond Energies

⚫ eg. C-H bond enthalpy in CH4

⚫ CH4 (g) → C (g) + 4 H (g) , at 298K.

⚫ Need: Hf of CH 4 (g) =- 75 kJ mol-1
⚫ Hf of H (g) = 218 kJ mol-1
⚫ Hf of C (g) = 713 kJ mol-1
⚫ Hdiss =  nHf (products) -  nHf ( reactants)
⚫ = 713 + ( 4x 218) – (- 75) = 1660 kJ
⚫ mol-1
⚫ Since have 4 bonds : C-H = 1660/4 = 415
⚫ kJ mol-1
Variation of H with temperature

Suppose do reaction at 400 K, need to know

Hf at 298 K for comparison with literature value. How?

⚫ As temp.î HmÎ ie. Hm  T

⚫  Hm = Cp,m  T where Cp,m is the molar

⚫ heat capacity at constant pressure.

⚫ Cp,m = Hm/ T = J mol-1/ K
⚫ = J K-1 mol-1
⚫   HT2 =  HT1 +  Cp ( T2 - T1)
⚫ Kirchoff’s equation.
⚫ and
⚫  Cp = n Cp(products)- nCp(reactants)

⚫ For a wide temperature range: Cp ∫ dT between T1 and T2.

⚫ Hence : qp = Cp( T2- T1) or H = Cp T and.
⚫
⚫ qv = Cv ( T2 – T1) or Cv T = U
⚫ ie. Cp = H / T ; Cv =U /T
⚫ For small changes:
⚫
⚫ Cp = dH / dT ; Cv = du / dT

⚫ For an ideal gas: H = U + p V

⚫ For I mol: dH/dT = dU/dT + R
⚫  Cp = Cv + R
⚫ Cp / Cv = γ ( Greek gamma)
Work done along isothermal paths

⚫ Reversible and Irreversible paths

⚫ ie T =0 ( isothermal)

⚫ pV = nRT= constant

⚫ Boyle’s Law : piVi =pf Vf

⚫ Can be shown on plot:

pV diagram
Pv
i i
P

pV= nRT = constant

Pv
f f

V
⚫ Work done = -( nRT)∫ dV/V

= - nRT ln (Vf/Vi)

⚫ Equation is valid only if : piVi=pfVf and therefore: Vf/Vi = pi/pf and

⚫ Work done = -( nRT) ln (pi/pf) and follows the path shown.

pV diagram

P PiVi
⚫ An irreversible path can be
followed: Look at pV Isothermal reversible process
diagram again. (ie. at equlb. at every stage
of the process)

PfVf

Irreversible reaction

V
An Ideal or Perfect Gas

⚫ NB
For an ideal gas, u = 0

Because: U  KE + PE
kT+ PE (stored in bonds)

Ideal gas has no interaction between molecules (no bonds broken

or formed)
Therefore u = 0 at T = 0

Also H = 0 since (pV) = 0 ie no work done

This applies only for an ideal gas and NOT a chemical reaction.
Calculation

⚫ eg. A system consisting of 1mole of perfect gas at 2 atm and

298 K is made to expand isothermally by suddenly reducing the
pressure to 1 atm. Calculate the work done and the heat that
flows in or out of the system.
⚫ w = -pex V = pex(Vf -Vi)
Vi = nRT/pi = 1 x 8.314 x (298)/202650
= 1.223 x 10-2 m3

Vf = 1 x 8.314 x 298/101325 = 2.445 x 10-2 m3

therefore, w = -pex (Vf- Vi)
= -101325(2.445-1.223) x 10-2 = -1239 J

U = q + w; for a perfect gas U = 0

therefore q = -w and
q = -(-1239) = +1239 J
Work done along adiabatic path

⚫ ie q = 0 , no heat enters or leaves the system.

⚫ Since U = q + w and q =0
⚫ U = w
⚫ When a gas expands adiabatically, it cools.
⚫ Can show that: pVγ = constant, where ( Cp/Cv =γ )
⚫ and: piViγ = pfVfγ and since:
⚫ -p dV = Cv dT
⚫ Work done for adiabatic path = Cv (Tf- Ti)
⚫ For n mol of gas: w = n Cv (Tf –Ti)
⚫ Since piViγ = pfVf γ

⚫ piViγ/Ti = pfVf γ/ Tf
⚫  T = T (V /V )γ-1
f i i f
⚫  w =n Cv{ ( Ti( Vi/ Vf)γ-1 – Ti}

⚫ An adiabatic pathway is much steeper than pV = constant

pathway.
Summary

⚫ piVi = pfVf for both reversible and irreversible

⚫ Isothermal processes.
⚫ For ideal gas: For T =0, U = 0, and H=0
⚫ For reversible adiabatic ideal gas processes:
⚫ q=0 , pVγ = constant and
⚫ Work done = n Cv{ ( Ti( Vi/ Vf)γ-1 – Ti}

⚫ piViγ = pfVfγ for both reversible and irreversible adiabatic ideal

gas.
2nd Law of Thermodynamics

⚫ Introduce entropy, S (state function) to explain spontaneous

⚫ change ie have a natural tendency to occur- the apparent

⚫ driving force of spontaneous change is the tendency of energy
⚫ and matter to become disordered. That is, S increases on
disordering.

⚫ 2nd law – the entropy of the universe tends to increase.

Entropy

⚫ S = qrev /T ( J K-1) at equilibrium

⚫ Sisolated system > 0 spontaneous change

⚫ Sisolated system < 0 non-spontaneous change

⚫ Sisolated system = 0 equilibrium

Properties of S

⚫ If a perfect gas expands isothermally from

⚫ Vi to Vf then since U = q + w = 0
⚫  q = -w ie
⚫ qrev = -wrev and
⚫ wrev = - nRT ln ( Vf/Vi)
⚫ At eqlb., S =qrev/T = - qrev/T = nRln (Vf/Vi)
⚫ ie S = n R ln (Vf/Vi)

⚫ Implies that S ≠ 0 ( strange!)

⚫ Must consider the surroundings.
Surroundings

⚫ Stotal = Ssystem + Ssurroundings

⚫ At constant temperature surroundings give heat to the system

to maintain temperature.
⚫  surroundings is equal in magnitude to heat gained or loss but
of opposite sign to make
⚫
⚫ S = 0 as required at eqlb.
⚫ Rem: dq = Cv dT and
⚫ dS = dqrev / T
⚫  dS = Cv dT/ T and
⚫ S = Cv ∫ dT /T between Ti and Tf
⚫ S = Cv ln ( Tf/ Ti )
⚫ When Tf/ Ti > 1 , S is +ve
⚫ eg. L → G , S is +ve
⚫ S → L , S is +ve and since qp = H
⚫ Smelt = Hmelt / Tmelt and
⚫ Svap = Hvap / Tvap
Third Law of Thermodynamics

⚫ eg. Standard molar entropy, SmThe entropy of a perfectly

crystalline substance is zero at T = 0

⚫ Sm/ J K-1 at 298 K

⚫ ice 45
⚫ water 70 NB. Increasing disorder
⚫ water vapour 189
⚫ For Chemical Reactions:
⚫ Srxn =  n S (products) -  n S ( reactants)

⚫ eg. 2H2 (g) + O2( g) → 2H2O( l ), H = - 572 kJ mol-1

Calculation

⚫ Ie surroundings take up + 572kJ mol-1 of heat

Srxn = 2S(H2Ol) - (2 S (H2g ) + S (O2g) )

⚫ = - 327 JK-1 mol-1 ( strange!! for a spontaneous
reaction; for this S is + ve. ).
⚫ Why? Must consider S of the surroundings also.
⚫ S total = S system + S surroundings
⚫ S surroundings = + 572kJ mol-1/ 298K = + 1.92 x 103JK-1 mol-1

 S total =( - 327 JK-1mol-1) + 1.92 x 103 = 1.59 x 103 JK-1 mol-1

⚫ Hence for a spontaneous change, S > 0
Free Energy, G

⚫ Is a state function. Energy to do useful work.

⚫ Properties
⚫ Since Stotal = Ssystem + Ssurroundings
⚫ Stotal = S - H/T at const. T&p
⚫ Multiply by -T and rearrange to give:
⚫ -TStotal = - T S + H and since G = - T Stotal

⚫ ie. G = H - T S

⚫ Hence for a spontaneous change: since S is + ve, G = -ve.

 Free energy

⚫ ie. S > 0, G < 0 for spontaneous change ;

⚫ at equilibrium, G = 0.

⚫ Can show that : (dG)T,p = dwrev ( maximum work)

⚫  G = w (maximum)
Properties of G

⚫ G =H -TS
⚫ dG = dH – TdS – SdT
⚫ H = U + pV
⚫ dH = dU + pdV + Vdp
⚫ Hence: dG = dU + pdV + Vdp – TdS – SdT
⚫ dG = - dw + dq + pdV + Vdp – TdS – SdT
⚫
⚫  dG = Vdp - SdT
For chemical Reactions:

⚫ For chemical reactions

⚫ G = n G (products) -  n G (reactants)

⚫
⚫ and

⚫ Grxn = Hrxn - T Srxn

Relation between Grxn and position of
equilibrium

⚫ Consider the reaction: A = B

⚫ Grxn = GB - GA

⚫ If GA> GB , Grxn is – ve ( spontaneous rxn)

⚫ At equilibrium, Grxn = 0.

⚫ ie. Not all A is converted into B; stops at equilibrium point.

Equilibrium diagram
For non-spontaneous rxn. GB > GA,
G is + ve
Gas phase reactions

⚫ Consider the reaction in the gas phase:

⚫ N2(g) + 3H2(g)→ 2NH3(g)

⚫ Q =( pNH3 / p)2 /( ( pN2/ p) (pH2/ p)3 ) where :

⚫ Q = rxn quotient ; p = partial pressure and p = standard

pressure = 1 bar
⚫ Q is dimensionless because units of partial pressure cancelled
by p .
⚫ At equilibrium:
⚫ Qeqlb = K = (( pNH3 / p)2 / ( pN2/ p) (pH2/ p)3 )eqlb
Activity ( effective concentration)

⚫ Define: aJ = pJ / p where a = activity or effective

concentration.
⚫ For a perfect gas: aJ = pJ / p
⚫ For pure liquids and solids , aJ = 1
⚫ For solutions at low concentration: aJ = J mol dm-3
⚫ K = a2NH3 / aN2 a3H2
⚫ Generally for a reaction:
⚫ aA + bB → cC + dD

⚫ K = Qeqlb = ( acC adD / aaA abB ) eqlb = Equilibrium constant

Relation of G with K

⚫ Can show that:

⚫ Grxn = Grxn + RT ln K

⚫ At eqlb., Grxn = 0

⚫  Grxn = - RT ln K

⚫ Hence can find K for any reaction from thermodynamic data.

⚫ Can also show that:

⚫ ln K = - G / RT

⚫ K = e - G / RT

⚫ eg
⚫ H2 (g) + I2 (s) = 2HI (g) , Hf HI = + 1.7 kJ mol-1 at 298K;
Hf H2 =0 ; Hf I 29(s)= 0
calculation

⚫ Grxn = 2 x 1.7 = + 3.40 kJ mol-1

⚫ ln K = - 3.4 x 103 J mol-1 / 8.314J K-1 mol-1 x 298K

⚫ = - 1.37
⚫ ie. K = e – 1.37 = 0.25
⚫
⚫ ie. p2 HI / pH2 p =0.25 ( rem. p = 1 bar; p 2 / p = p )

⚫  p2 HI = pH2 x 0.25 bar

Example: relation between Kp and K

Consider the reaction:

N2 (g) + 3H2 (g) = 2NH3 (g)

Kp =( pNH3 / p)2 / ( pN2/ p )( pH2 / p)3

and

K = [( pNH3 / p)2 / ( pN2/ p )( pH2 / p)3] eqlb

 Kp = K (p)2 in this case. ( Rem: (p)2 / (p)4 = p -2

⚫ For K >> 1 ie products predominate at eqlb. ~ 103

⚫ K<< 1 ie reactants predominate at eqlb. ~ 10-3

⚫ K ~ 1 ie products and reactants in similar amounts.

Effect of temperature on K

⚫ Since  Grxn = - RT ln K = Hrxn - TSrxn

⚫ ln K = - Grxn / RT = - Hrxn/RT + Srxn/R

⚫  ln K1 = - Grxn / RT1 = - Hrxn/RT1 + Srxn/R

⚫ ln K2 = - Grxn / RT2 = - Hrxn/ RT2 + Srxn/ R

⚫
⚫ ln K1 – ln K2 = - Hrxn / R ( 1/ T1 - 1/ T2 ) 0r

⚫ ln ( K1/ K2) = - Hrxn / R ( 1/ T1 - 1/ T2 ) van’t Hoff equation