Chem 17

Sean See
T337
sasee@up.edu.ph
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
U = internal 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 = mcT

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

-q = heat released (Tf<Ti)

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

q = mcT
qrxn (known) = qcal = CcalT
Solve for Ccal

Given Ccal and T, get qrxn(unknown)

Thermochemistry
Work expansion against external pressure

w = -Pext V

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

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

U = q + w
Thermochemistry
First Law of Thermodynamics

For an isolated system

U = 0
Thermochemistry
State functions functions that depend only on the
initial and final states. (Path independent)

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

Path dependent functions functions which depend

on the processes the system undergoes

q, w
Thermochemistry
Expansion by reduction of pressure
1 step w 2 steps w
2.40 > 1.20 1.20 ( V ) 2.40 > 1.80 1.80 ( V1 )
1.80 > 1.20 1.20 ( V2 )
Thermochemistry
Constant Volume Processes

U = q + w = q + 0
U = qv
Thermochemistry
Constant Pressure Processes

U = qp + w
U = qp - PextV
qp = U + PextV
qp = H
Thermochemistry
Direction of Heat Flow
Hreverse = - Hforward

Extrinsic Property
A + B -> AB H
2A + 2B -> 2AB 2H
Thermochemistry
Enthalphy of changes in state enthalphy associated
with a phase change

H2O(l) -> H2O(g)

Hv = enthalphy of vaporization

H2O(l) -> H2O(s)

Hf = enthalphy of fusion
Thermochemistry
Enthalphy of reaction (H) heat produced or
consumed by chemical reaction
Hrxn = npHoProducts - nrHoReactants

Standard enthalphy of formation (Hf0) 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
Hrxn = nHoProducts - nHoReactants
Thermochemistry
Hess Law
Thermochemistry
Hess Law
Thermochemistry
Hess Law
Thermochemistry
Hess Law
Thermochemistry
Bond Enthalpies

Hrxn = n(bonds broken) n(bonds formed)

Thermochemistry
Spontaneous Change
S = entropy (related to disorder)
S > 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 = Boltzmanns constant
qrev
S = (thermodynamic entropy)
T
valid for isothermal and reversible heat exchanges
Entropy
S = klnW
Sf = klnWf
Si = klnWi
Wf ni
S = kln kln
Wi nj
ni qkT rev
=e
nj
qrev
S = kln(e kT )
qrev qrev
S = k =
kT T
Evaluating S
Htransition
Stransition =
Ttransition

S = npSproducts - nrSreactants
Criteria for Sponteneity
G = H TS

G = 0 System in equilibrium
G < 0 Process is spontaneous
G > 0 Process is non spontaneous
Evaluating G
Go = Ho TSo
Ho = npHoproducts - nrHoreactants
So = npSoproducts - nrSoreactants

Go = npGoproducts - nrGoreactants
G in non standard conditions
Go = Ho TSo vs G = H TS

Under non standard conditions

H = Ho

S= So - Rln = So RlnP (Po = 1atm)

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

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

H = Ho = 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)

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

3
P N P H
S = So - Rln P 2NH 22
3
G in non standard conditions
H = Ho
3
P N P H
S = So - Rln 2 2
P NH3 2
3
o o P N2 P H2
G = H - T(S - Rln )
P NH3 2
G = Go + RTlnQ

Q = reaction quotient =

G in non standard conditions
At equilibrium

G = Go + RTlnQ = 0
Go = -RTlnKeq
Equilibrium Constant
For ideal solutions/ gases
M
Keq = Kc =
M

P
Keq = Kp =
P
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
+ = Kf
Cu NH3 6
Equilibrium Constant
For non-ideal solutions/gases

Keq = ( = activity)

M P
= or
Mo Po

Where Mo is the standard molarity 1M

Where Po is the standard pressure 1atm
Equilibrium Constant
Keq and Temperature
Go = -RTlnKeq = Ho - TSo

Ho So
lnKeq = +
RT R

Evaluating Keq when T changes

Ho So Ho So
lnKeqf lnKeqi = + +
RTf R RTi R
Keqf Ho 1 1
ln = (Vant Hoff Equation)
Keqi R Tf Ti
Keq and Temperature
Keq and Temperature

Ho So
lnKeq = +
RT R

Plot lnKeq vs 1/T

Ho
slope =
R o
S
Intercept =
R
Coupled Reactions
Cu2O(s) -> 2Cu(s) + O2 (g) Go = 125 KJ
C(s) + O2 (g) -> CO (g) Go = -175 KJ
---------------------------------------------------------------------
Cu2O(s) + C(s) -> 2Cu(s) + CO (g) Go = -50 KJ
 Ellingham
Diagram
Shows plots of G and T
1. Lower line = more stable oxide
2. Lower line will reduce higher
line
3. Bigger gap between lines
means easier reduction
Summary
U = q + w
q = mcT
w = -PextV

U = -PextV (T = 0)
U = qv (V = 0)
H = qp = U + PextV (P = 0)
Summary
Evaluating H
Hess Law
Horxn = npHoProducts - nrHoReactants
Hotransition
Hrxn = n(bonds broken) n(bonds formed)
H = Ho
Summary
Evaluating S
Sorxn = npSoProducts - nrSoReactants
Wf
S = kln
Wi
qrev
S =
T
Htransition
Stransition =
Ttransition

P
S= So - Rln = So RlnP (Po = 1atm)
Po
Summary
Evaluating G
Go = Ho TSo
Go = npGoproducts nrGoreactants
Go = -RTlnKeq (At equilibrium)

Keq = Kc or Kp

Keqf Ho 1 1
ln = (Vant Hoff Equation)
Keqi R Tf Ti