Chem 17

Sean See
T337
sasee@up.edu.ph
Thermochemistry
Thermodynamics

Study of the changes in energy that accompany

physical and chemical processes
Thermochemistry
• System – what you are looking at
• Surrounding – everything else
• Boundary – what is between the system and
surrounding
Thermochemistry
• Types of System (by type of boundery)
• Open – allows flow of matter and energy
• Closed – allows flow of energy only
• Isolated – no flow of matter or energy
Thermochemistry
Thermodynamic Terminology

Greek isos: equal

baros: weight
adiabatos: not passable
-----------------------------------------------------
Isothermal: Constant temperature
Isobaric: Constant pressure
Isochoric: Constant volume
Adiabatic: No heat flow (Q = 0)
Thermochemistry
Thermodynamic Parameters

U = internal energy (total energy)

q = heat (thermal energy)
w = work (mechanical energy)
Thermochemistry
Kinetic Energy
2
1 m
ek = mv2 [ek ] = kg = J
2 s

Work

w=Fxd
m m
= mxaxd [w ] = kg 2 = J
s
Thermochemistry
q = mcΔT

m = mass (g)
c = specific heat capacity
ΔT = change in temp

-q = heat released (Tf<Ti)

q = heat absorbed (Tf>Ti)
Thermochemistry
Calorimetry – measurement of heat

q = mcΔT
qrxn (known) = qcal = CcalΔT
Solve for Ccal

Given Ccal and ΔT, get qrxn(unknown)

Thermochemistry
Work – expansion against external pressure

w = -Pext ΔV

-w = work done by system (Vf>Vi)

w = work done on system (Vf<Vi)
Thermochemistry
Internal Energy – energy content of system

ΔU = q + w
Thermochemistry
First Law of Thermodynamics
"Energy can neither be created nor destroyed, but only transferred from
one system to another and transformed from one form to another."

or

"The internal energy of an isolated system is constant (even though that

energy may be transformed from one type to another)."

Change in Internal
∆U = q + w Energy of system or ∆U:
∆U > 0 gain of energy
∆U < 0 loss of energy
ΔU = 0 Isolated System
Thermochemistry
State functions – functions that depend only on the
initial and final states. (Path independent)

U, H, G, S, P, T, V

Path dependent functions – functions which depend

on the processes the system undergoes

q, w, n
Thermochemistry
Expansion by reduction of pressure
1 step w 2 steps w
2.40 –> 1.20 1.20 ( ΔV ) 2.40 –> 1.80 1.80 ( ΔV1 )
1.80 –> 1.20 1.20 ( ΔV2 )
Thermochemistry
Constant Volume Processes

ΔU = q + w = q + 0
ΔU = qv

Heat measured at constant volume gives ΔU

Measuring at constant volume is done by bomb
calorimetry
Thermochemistry
Constant Pressure Processes

ΔU = qp + w
ΔU = qp - PextΔV
qp = ΔU + PextΔV
qp = ΔH

Heat measured at constant pressure gives ΔH

Thermochemistry
Direction of Heat Flow
ΔHreverse = - ΔHforward
ΔH < 0 -> exothermic
ΔH > 0 -> endothermic

Enthalpy Extrinsic Property

A + B -> AB ΔH
2A + 2B -> 2AB 2ΔH
Thermochemistry
Types of Enthalpy

Enthalpy associated with phase changes

Enthalpy of reaction
Thermochemistry
Enthalphy of changes in state – enthalphy associated
with a phase change

H2O(l) -> H2O(g)

ΔHv = enthalphy of vaporization

H2O(l) -> H2O(s)

ΔHf = enthalphy of fusion

Processes which separate particles are endothermic

Thermochemistry
Enthalphy of reaction (ΔH) – heat produced or
consumed by chemical reaction
ΔHrxn = ΣnpHoProducts - ΣnrHoReactants

Standard enthalphy of formation (ΔHf0) – enthalphy

associated with the formation of a compound from
the elements in their standard states

Standard enthalphies of formation of the elements in

standard states is zero 0
Thermochemistry
ΔHrxn = ΣnHoProducts - ΣnHoReactants
Thermochemistry
Hess’ Law
Thermochemistry
Hess’ Law
Thermochemistry
Hess’ Law
Thermochemistry
Hess’ Law
Thermochemistry
Bond Enthalpies

ΔHrxn = Σn(bonds broken) – Σn(bonds formed)

Thermochemistry
Spontaneous Changes
• S = entropy (related to disorder)
• ΔS > 0: process is spontaneous
• Processes which increase entropy
• Pure liquids or liquid solutions are formed from solids
• Gases are formed from either solids or liquids
• The number of molecules of gas increases as a result of
a chemical reaction
• The temperature of a substance increases
Spontaneous Changes
• S = klnW (statistical entropy)
• W = number of possible states
• k = Boltzmann’s constant
qrev
• ΔS = T
(thermodynamic entropy)
• valid for isothermal and reversible heat exchanges
Entropy
S = klnW
Sf = klnWf
Si = klnWi
Wf ni
ΔS = kln ≈ kln
Wi nj
ni qkT rev
=e
nj
qrev
ΔS = kln(e kT )
qrev qrev
ΔS = k kT = T
Evaluating ΔS
ΔHtransition
ΔStransition = T
transition

ΔS = ΣnpSproducts - ΣnrSreactants
Criteria for Sponteneity
ΔG = ΔH – TΔS

ΔG = 0 System in equilibrium
ΔG < 0 Process is spontaneous
ΔG > 0 Process is non spontaneous
Evaluating ΔG
ΔGo = ΔHo – TΔSo
ΔHo = ΣnpHoproducts - ΣnrHoreactants
ΔSo = ΣnpSoproducts - ΣnrSoreactants

ΔGo = ΣnpGoproducts - ΣnrGoreactants

ΔG in non standard conditions
• ΔGo = ΔHo – TΔSo vs ΔG = ΔH – TΔS

Under non standard conditions

• ΔH = ΔHo
𝑃
•S= So - Rln𝑃 = So – RlnP (Po = 1atm)
𝑜

N2(g) + 3 H2(g) -> 2 NH3(g)

ΔG in non standard conditions
N2(g) + 3 H2(g) -> 2 NH3(g)

ΔH = ΔHo = 2(Ho(NH3(g))) – 1(0) – 3(0) = 2 Ho(NH3(g))

S = So - RlnP

S(N2) = So(N2) – RlnP(N2)

S(H2) = So(H2) – RlnP(H2)
S(NH3) = So(NH3) – RlnP(NH3)

ΔS = 2[So(NH3) – RlnP(NH3)] – [So(N2) – RlnP(N2)] – 3[So(H2) – RlnP(H2)]

3
P N P H
ΔS = ΔSo - Rln P 2NH 22
3
ΔG in non standard conditions
ΔH = ΔHo
3
P N P H
ΔS = ΔSo - Rln P 2NH 22
3
3
o o P N2 P H2
ΔG = ΔH - T(ΔS - Rln P NH 2 )
3

ΔG = ΔGo + RTlnQ
𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠
Q = reaction quotient = 𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
ΔG in non standard conditions
At equilibrium

ΔG = ΔGo + RTlnQ = 0
ΔGo = -RTlnKeq
Equilibrium Constant
For ideal solutions/ gases
ΠM𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠
Keq = Kc = ΠM𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

ΠP𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠
Keq = Kp = ΠP𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
Equilibrium Constant
CH3COOH(aq) -> H+(aq) + CH3COO-(aq)
+ −
H [CH3COO ]
Keq = = Ka
[CH3COOH]

Cu2+(aq) + 6NH3 (aq) -> Cu(NH3)42+(aq)

+
2
Cu NH3 4
Keq = 2
+
6 = Kf
Cu NH3
Equilibrium Constant
For non-ideal solutions/gases
Πα𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠
Keq = Πα𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
(α = activity)

M P
α= or
Mo Po

Where Mo is the standard molarity 1M

Where Po is the standard pressure 1atm
Equilibrium Constant
Keq and Temperature
ΔGo = -RTlnKeq = ΔHo - TΔSo

ΔHo ΔSo
lnKeq =− RT + R

Evaluating Keq when T changes

ΔHo ΔSo ΔHo ΔSo

lnKeqf – lnKeqi =− RT + R + RT − R
f i

Keqf ΔHo 1 1
lnK = − R T − T (Van’t Hoff Equation)
eqi f i
Keq and Temperature
Keq and Temperature

ΔHo ΔSo
lnKeq =− RT + R

Plot lnKeq vs 1/T

ΔHo
slope = − R
ΔSo
Intercept =
R
Coupled Reactions
Cu2O(s) -> 2Cu(s) + ½ O2 (g) ΔGo = 125 KJ
C(s) + ½ O2 (g) -> CO (g) ΔGo = -175 KJ
---------------------------------------------------------------------
Cu2O(s) + C(s) -> 2Cu(s) + CO (g) ΔGo = -50 KJ
 Ellingham
Diagram
Shows plots of ΔG and T
1. Lower line = more stable oxide
2. Lower line will reduce higher
line
3. Bigger gap between lines
means easier reduction
Summary
ΔU = q + w
q = mcΔT
w = -PextΔV

ΔU = -PextΔV (ΔT = 0)
ΔU = qv (ΔV = 0)
ΔH = qp = ΔU + PextΔV (ΔP = 0)
Summary
Evaluating ΔH
Hess’ Law
ΔHorxn = ΣnpHoProducts - ΣnrHoReactants
ΔHotransition
ΔHrxn = Σn(bonds broken) – Σn(bonds formed)
ΔH = ΔHo
Summary
Evaluating ΔS
ΔSorxn = ΣnpSoProducts - ΣnrSoReactants
Wf
ΔS = klnW
i
qrev
ΔS = T
ΔHtransition
ΔStransition =
Ttransition

P
S= So - RlnP = So – RlnP (Po = 1atm)
o
Summary
Evaluating ΔG
ΔGo = ΔHo – TΔSo
ΔGo = ΣnpGoproducts – ΣnrGoreactants
ΔGo = -RTlnKeq (At equilibrium)
Πα𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠
Keq = ≈ Kc or Kp
Πα𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

Keqf ΔHo 1 1
ln =− − (Van’t Hoff Equation)
Keqi R Tf Ti