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∆H o298 (reaction) = ∑ ν ∆H
i
o
f ,298 ( products) − ∑ ν ∆H
i
o
f ,298 ( reactants)
AT 25 °C !
1
The Second Law of Thermodynamics
Spontaneous processes are those which increase the
entropy of the Universe
∆S = Sfinal - Sinitial
q rev
∆S =
T
2
Entropy changes in chemical reactions
AT 25 °C !
G = H – TS or ∆ G = ∆ H - T ∆S
3
Entropy as a predictor of chemical reactivity
This is for the H2 / O2 / H2O system. The 2nd Law refers to the
entropy of the Universe increasing as a requirement for
spontaneity.
4
Balloon containing
H2(gas) + spark!
∆rH°° (system) = -
571.6 kJ
HEAT
∆rH° (surroundings =
+ 571.6 kJ
5
The Gibbs function or Gibbs free energy, G.
So we can write
∆H - T ∆S < 0
G = H – TS or ∆ G = ∆ H - T ∆S
∆G)p, T < 0
(∆
6
In general, we can conclude that if a process or reaction results
in a lowering of the free energy, it will be spontaneous i.e. that it
will be favourable and CAN happen. It does not mean that it
WILL happen.
7
Key points so far:
8
Calculate the Gibbs free energy change at 298 K and estimate the
temperature at which the reaction just becomes spontaneous.
Solution
∆ r H 298
o
= ∑ν i ∆ f H 298
o
( products ) − ∑ν i ∆ f H 298
o
( reactants)
∆ r S 298
o
= ∑ν i S o298 ( products ) − ∑ν i S 298
o
( reactants)
• calculate ∆rG°298
9
∆rG = 0
∆rH - T ∆rS = 0
• Rearrange to find T
+ 467.9kJmol −1
558.4 × 10 −3 kJmol −1 K −1 = (T / K)
T = 838 K
10
Variation of enthalpy with temperature
dq p dH
C p = =
dT p dT p or dH = Cp dT
T2
∫ dH = ∫C
T1
p dT
the Kirchoff Equation
11
Approximation: treat cp as independent of T for small temp.
ranges and use the average value over the range of T
H − H = C p (T2 − T1 )
T2 T1
12
Enthalpies of Reaction
A model reaction: R → P
The enthalpy of R at 25 °C is ∆H°f, 298 (R).
where
∆C p = ∑ν i Cp (products) - ∑ ν i Cp (reactants)
13
The complete combustion of ethane releases 1558.8 kJ mol-1 at 25 °C.
Calculate ∆H°(combustion) at 100 °C.
cp / J K-1 mol-1: C2H6(g) 52.6; O2(g) 29.4; CO2(g) 37.1; H2O(l) 75.3
_____________________________________________________
___________________________________________________
14
N2(g) + 3 H2(g) → 2 NH3(g)
∆H°298 = [ 2 x ∆H°f, 298 (NH3)] - [∆H°f, 298 (N2) + 3 ∆H°f, 298 (H2)]
= [ - 92.0 ] - [ 0 ] kJ mol-1
Hence, at 450 °C, 108.24 kJ is evolved for each mole of the equation
i.e 108.24 kJ is evolved per mole of nitrogen which reacts.
Since, for a gas, volume ∝ number of moles, the 1:3 mixture is in the
stoichiometric amount. At 0 °C and 1 atm pressure, 1 mole occupies
22.4 dm3. Thus, the total amount of gas passing over the catalyst
amounted to 5 moles per minute, of which 1.25 moles were N2.
15
Effect of temperature on entropy
From before, we know that:
Tf
1 T
S T f = S Ti + c p ∫ dT = S Ti + c p ln f
Ti
T Ti
16
Given the heat capacities of ice and water at 0 °C are 2.2 and
4.18 J K-1 g-1 and the enthalpy of fusion is 332 J g-1, calculate
the entropy change for the freezing of 1 mole of supercooled
water at -10 °C.
_________________________________________________
∆S ∆S ∆S
water, -10 oC
1
→water, 0 oC
2
→ice, 0 oC
3
→ice, -10 oC
Hence,
17
Standard or Absolute Entropies
For convenience, entropies are listed under standard
conditions.
Tm
c p (solid )
1. Heating from 0K to Tm. ∆S o 1 =
∫ T
dT
0
o ∆H fus.
2. Melting at Tm ∆S 2 =
Tm
Tb
c p (liquid )
3. Heating from Tm to Tb ∆S o 3 =
∫ T
dT
Tim
o ∆H vap.
4. Vaporization at Tb ∆S 4 =
Tb
298
c p ( vapour )
∫
o
5. Heating from Tb to 298 K ∆S 5 = dT
T
Tb
18
Where there is more than one phase in the solid, the
additional ∆S entropy for the phase changes must also be
taken into account.
T2
∆c p
∆ S T2 = ∆ S T +
1 ∫ T
dT
T1
19
Using mean heat capacities,
T2
T2
1
∆ S T2 = ∆ S T1 + ∆ c p ∫ dT = ∆ S T1 + ∆ c p ln
T1
T T1
20
Variation of Gibbs free energy with conditions
Substituting this:
dG = VdP - SdT
dG = VdP - SdT
21
How can we use the Master equation?
Variation of G with temperature
dG = VdP – SdT
at constant pressure: dP = 0
dG
= −S
dG = - S dT or dT P
d ∆G
For chemical reactions, = − ∆S
dT P
22
Given the pure component data below, calculate the standard free
energy change for the following reaction at 25 °C and 1025 °C.
MgO(s) + CO(g) → Mg(s) + CO2(g)
23
Variation of G with pressure
dG = VdP – SdT
At fixed temperature, dT = 0.
dG
=V
dG = VdP or dp T
dG nR T
= V =
For an ideal gas. dp T p
p2
G 2 − G 1 = nRT ln
which leads to p1
24
G° is the value at the standard pressure of p° = 1 bar.
25
Variation of G with concentration
26
Free energy and equilibrium
The free energy of the system will change throughout a reaction
depending on the amounts of reactants and products.
27
28
This schematic approach allows us to define one of the
fundamental statements of chemistry
(a C ) γ (a D )δ
Q =
(a A )α (a B )β
γ
( a C ) eqm (a D ) δeqm
Q eqm = = K eqm
( a A ) αeqm ( a B )βeqm
∏ 15 ( a i ) = a 1 × a2 × a3 × a4 × a5
29
Different types of equilibrium constant can be defined:
If Keqm is calculated from gas pressures - Kp.
If calculated from concentrations - Kc.
Examples.
( p N H 3 ) 2eqm
Kp =
N2(g) + 3 H2(g) ↔ 2 NH3(g) ( p H 2 ) 3eqm ( p N 2 ) eqm
(a CaCO 3 ) 1 1
Kp = = =
( pCO 2 ) eqm (a CaO ) ( pCO 2 ) eqm (1) ( pCO 2 ) eqm
30
The definitions of Q and Keq allow us to predict the direction of a
chemical reaction. We can say that:
31
aC aD
= {(G°C + G°D ) - (G°A + G°B )} + RT ln a a
A B
− ∆G o
K eqm = exp
RT
32
Gibbs Free Energy and Reactivity
We know that if ∆G° < 0, Keqm > 1 so the forward reaction takes
place. The products will be present in larger concentration than
the reactants at equilibrium. Can we quantify this?
∆G°°/ -23 0 + 23
-1
kJ mol
33
Pause for breath – where are we ?
34
Silver carbonate decomposes on heating. Calculate the equilibrium
constant at 110 °C for the reaction.
− ∆G o − 14.71 x 103
K p = exp = exp = 9.87 x 10- 3
RT (8.314)(383.15)
If the conditions in the oven are such that the partial pressure of
CO2 is > 9.9 x 10-3 (or ∼ 1% by volume) then the silver carbonate
will not decompose.
35
Relating the Equilibrium Constant to Experiment
Take an example:- gas phase reaction:
N2O4(g) ↔ 2 NO2(g)
36
From now on, we need some algebra.
4α 2 Ptot 2 (1 + α ) 4α 2 Ptot
Kp = =
(1 − α )(1 + α ) 2 Ptot (1 − α )(1 + α )
4 α 2 P to t
K p =
or (1 − α 2 )
37
Many stoichiometries give rise to quadratic or cubic equations.
38
Formulate expressions in terms of the degree of dissociation for the
equilibrium constants for the following reactions.
(a) If we start with 1 mole Ni(CO)4(g) and α react, then at eqm., 1-α
moles remain. α moles of Ni(s) together with 4α moles of CO form.
When considering Kp, only gases contribute to the partial pressures.
The total number of gas moles = (1-α) + 4α = (1+3α)
4
4α 4
(1) Ptot
(1) (p CO ) 4 1 + 3α ( 4α ) 4 (1 + 3α ) Ptot
3 3
256 α 4 Ptot
Kp = = = =
p Ni ( CO ) 4 1− α (1 − α )(1 + 3α ) 4 (1 − α )(1 + 3α ) 3
P
1 + 3α tot
(b) The only gas involved is O2. Thus, since the activity of solids is 1
and the only gas present is oxygen,
( a Hg ) 2 (p O 2 ) (1) 2 (p O 2 )
Kp = = = Ptot
( a HgO ) 2 (1) 2
(c) If the initial concentration is c mol dm-3 and α is the fraction which
reacts, at equilibrium there will be (αc) mol dm-3 of H+, (αc) mol
dm-3 of CH3COO- and (1-α)c mol dm-3 of CH3COOH. Thus
[ H + ] [CH 3 COO − ] ( α c ) ( α c ) α 2 c
Kc = = =
[ CH 3 COOH ] (1 − α ) c 1− α
39
Effect of conditions on reaction yields and Keqm
Effect of pressure
40
Effect of temperature
Since ∆G° = ∆H° - T∆S° = - RT ln Keqm,
− ∆G o − ∆H o T∆So
ln K eqm = = +
RT RT RT
∆So ∆H o
or
ln Keqm = −
R RT
41
Le Chatelier’s principle
The above provides the explanation of a principle suggested by
Le Chatelier on the basis of empirical observations.
42
In the vapour, acetic acid partially associates into dimers. At a total
pressure of 0.2 bar, acetic acid is 92% associated at 25 °C and 82%
associated at 45 °C. Calculate the enthalpy and entropy changes for
the association reaction. What will be the effect on the dissociation of
changing the total pressure?
______________________________________________________
If we begin with 100 mol and 92% dimerises, 8 mol remain at eqm.
The 92 mol which react give rise to 46 mol of dimer. The total number
of moles present is therefore 54.
K eq (T2 ) ∆H o 1 1 37.33 ∆ H o
1 1
ln = − ; ln = −
K (T ) R T T 194.1 8.314 298.15 318.15
eq 1 1 2
43
Applying Le Chatelier’s principle, an increase of pressure should favour
the side of the reaction with the lower number of gas moles i.e. favour
the dimerisation.
and solve simultaneously assuming that ∆H° and ∆S° do not vary with
temperature.
44
Chemical potential
Earlier, we made the assumption that GA = G° + RT ln aA
in a mixture
e.g. think about 1 mole of water. Will the free energy change
will be the same if it is added to a large amount of water, or
benzene, or ethanol or sulphuric acid?
45
If we have a large amount of a substance, B, and we add an
amount dnA moles of A, then the free energy change at
constant T, p, dG, is
dG = µA dnA
Why is µ important ?
G = G° + nRT ln ( p / p°).
µA = µA ° + RT ln ( pA / pA°)
46
Also, since dG = 0 at equilibrium.
0 = (µA (-dn)) + µB dn
or
µA dn = µB dn or µ A = µB
47
The chemical potential can be
thought of as the “driving force” for a
chemical process. µ is equivalent to
the slope of the Gibbs free energy
versus composition curve.
48
Kinetics and Thermodynamics of Equilibrium
We are concentrating on thermodynamic aspects of equilibrium.
Perhaps easier is the kinetic approach.
Thus, the ratio of the forward and reverse rate constants also
gives the equilibrium constant.
49
The standard enthalpy of formation of water is -241.8 kJ mol-1. Use
mean heat capacities and standard entropies to estimate the
percentage dissociation of water vapour at 2000 °C and 0.01 bar
pressure.
_________________________________________________________
50
1 1
( p H 2 )( p O 2 ) 2 ( x H 2 p tot )( x O 2 p tot ) 2
Kp = =
(p H 2O ) ( x H 2 O p tot )
(0.5 α ) 2 (1 + 0.5α ) p 2
1 3 3 1
(α ) 0.5 α 2 p 2
= =
(1 + 0.5α ) (1 + 0.5α ) 1 2 (1 - α ) p 1
(1 - α ) (1 + 0.5α ) 2
3 1
0.5 α 2 p 2 3
Kp = = 0.7071 (0.1) α 2 = 2.47 x 10 3
1
51
Electrochemical cells
An important class of reaction not so far discussed is that of
electron transfer or redox reactions.
52
There must be a net balance of electrons and so both must
take place concurrently, hence the name redox reaction.
Read…..
53
Standard electrode potentials
The voltage generated clearly depends on the nature of the two
half cells. Again, we need to fix a standard.
54
The e.m.f. of the cell, E, tells us about the tendency for
electrons to flow around the circuit - the same as the tendency
for the redox reaction to occur - so it must be related to the
reaction free energy
∆G° = - n ℑ E°
56
Thermodynamic measurements by electrochemistry
dG d∆G o
= −S or ∆S = −
o
We already know that dT P dT p
dE o
∆S = nℑ
o
dT p
57
An electrochemical cell with the following reaction generates a
standard electrode potential of 1.055 V at 25 °C and 1.015 V at
0°C. Calculate the standard enthalpy, entropy and free energy
changes for the reaction at 25 °C.
dE o 1.055 − 1.015
∆S = nℑ
o = ( 2) (96485) = 308.75 J K -1
mol -1
298.15 − 27315
.
dT p
58
Concentration dependence of electrode potentials
We saw earlier that the free energy change for reactions in
solution can be described by
∆G = ∆G° + RT ln Q
Substituting for the free energy in terms of electrode potentials,
RT o
E=E − ln Q
n ℑ E = - n ℑ E° + RT ln Q or nℑ
RT RT a Cu a Zn 2+
E=E − o
ln Q = E −
o
ln
nℑ nℑ a Cu 2+ a Zn
(8.314JK −1mol−1 )(298K ) (1)(0.1)
E = 1.1 - −1
ln
(2)(96485Cmol ) (0.005)(1)
Hence, E = 1.061 V
59
When the cell reaction reaches equilibrium, Q = Keqm and
electron flow stops and E = 0. Thus, it follows that
RT
Eo = ln K eq
nℑ
This provides a very convenient method for estimating the
equilibrium constants and standard free energy changes since
E° values are available for a very wide range of reactions.
pH = - log10 [H+]
60
Where could we go from here
We have discussed a small number of applications of
equilibrium constants and electrode potentials. The aim was to
introduce the basic principles. There are many other areas of
chemistry where related principles can be applied and you
should be aware of these from reading textbooks. These
include: acid-base equilibria, solubility of salts and other
compounds.
61