Chem 17 Concepts and Equations

1st LE topics

Types of systems

Transfer of energy
heat or q
q = mcT for homogenous systems
q = CT for heterogenous systems
q = Hphase change mol substance for phase changes

work or w
w = -PV pressure-volume work
(V = Vfinal Vinitial)

 1st Law of Thermodynamics: U = q + w

U
change in internal energy
- energy at constant volume condition (isochoric energy)
- obtained using a bomb calorimeter

ENTHALPY, H

H > 0 - exothermic
H < 0 - endothermic
H = 0 - athermic

The heat obtained at constant pressure is the enthalpy of

the system: H = qp

The enthalpy change, H, is the change in heat content at

constant pressure.

H = (qf qi)p

For chemical systems, the molar enthalpy change, is the

change in heat content at constant pressure per mole.

H =

 
 


Calculating Enthalpy of reaction

Hrxno =  ()  ( )
from heats of formation or Hfo

H rxn =

H rxn =

T(C cal + m H 2O c H 2O + m species cspecies )

n LR

T(C cal + m species cspecies )

n LR

water solvent as
separate acceptor of
heat

other pure species
formed or in excess in
the reaction

other pure species formed or in

excess in the reaction

from constant-pressure (isobaric) calorimetry)

Given the following enthalpies of formation:

[1] 2 Fe(s) + O 2(g) 2 FeO(g)

[2] 4 Fe(s) + 3 O 2(g) 2 Fe2O3(s)
Determine the Hrxn for :
Balance the reaction first!

H o = 544 kJ
H o = 1648 kJ

FeO (s) + O 2(g) Fe 2 O 3 (s)

Enthalpy
follows Hess
Law of Heat
Summation

4FeO(s) + O 2(g) 2Fe 2O3(s)

Arrange reactions [1] and [2] so that they also have FeO and O2 as reactants and
Fe2O3 as a product.
Each reaction can be doubled, tripled, or multiplied by half, etc.
The Ho values are also doubled, tripled, halved, etc.
If a reaction is reversed the sign of the Ho is changed.
For [1]: reverse, 2[-1] 2 (2 FeO (s) 2 Fe (g) + O 2(g) )
multiply by 2

2[-1] 4FeO (s) 4Fe (g) + 2O 2(g)

For [2]: retain

H o = 2(+544 kJ/mole)
H o = +1088 kJ/mole)

[2] 4Fe (s) + 3O 2(g) 2Fe 2 O 3(s)

H o = 1648 kJ

4FeO (s) + O 2(g) 2Fe 2 O 3 (s)

H rxn = -568 kJ/mole

For gaseous reactions (all reactants and products gases)

Hrxno = nBE

!

mBE#$%&!

requires good knowledge of Lewis structures

Relationship of H and U:
For reactions with gases:
H= U + (ngas)RT
where ngas = (total moles coefficient of gaseous products) (total
moles of coefficient gaseous reactants)
For reactions without gases:
H = U

S > 0 - greater disorder

S < 0 - decrease disorder

ENTROPY, S

2nd Law of thermodynamics:

In spontaneous changes the universe tends towards a
state of greater disorder
(reactions that result in greater disorder are more favored)

3rd Law of Thermodynamics:

The entropy of a pure, perfect, crystalline solid at 0 K is
zero
- allows calculation of Srxno

o
rxn

= n

o
products products

o
reactants reactants

GIBBS FREE ENERGY, G

G > 0 greater disorder
G < 0 decrease disorder
G = 0 equilibrium

o
rxn

= n productsG

o
f products

n reactantsG

o
f reactants

Free Energy of a system can be calculated from

the Disorder and Enthalpy of the system

G = H TS

G = H TS
H S
G
Reaction spontaneity

Spontaneous at all Ts

Temp dependent
Spont at low T
+
+
Temp dependent
Spont at high T
+

+
NON Spont at all Ts

 Thermodynamic functions at Standard Conditions

Go = Ho TSo
Go = n#$% G $0(products) m G $0(reactants)
Ho = n#$% H $0(products) m H $0(reactants)
So

= n#$% S $(products) + m S $(reactants)

Rate of Reaction
aA(aq) + bB(aq) cC(aq) + dD(aq)
Rate of a reaction can be written as:

1 [A ]
1 [B]
1 [C]
1 [D]
Rate =
=
= +
=+
a t
b t
c t
d t
In terms of reactants

In terms of products

Types of reaction based on Rate law

Expressions
Reaction

Possible
Experimental Rate
Law

Order of Reaction

Unit of k (when t in
secs)

A  products

Rate = k

Zero order

M/s

A  products

Rate = k[A]

First order wrt [A],

First order overall

1/s

A  products

Rate = k[A]2

2nd order wrt [A],

2nd order overall

1/Ms

Rate = k[A][B]

1st order wrt [A], 1st

order wrt [B], 2nd
order overall

1/Ms

A + B  products

Differential and Integral Rate Law Forms

Reaction

Possible
Experimental
Rate Law

Differential
Rate law form

A  products

Rate = k
(zero order)

[A ]
=k
t

[A ]

= k[A]
t

Integral Rate
(linearized form:
y = mx + b)

[A] = [A]0 - k t

Half-life

t1 =
2

ln[A] = k t+ ln[A]0 t 1

A  products

Rate = k[A]
1st order wrt A

A  products

Rate = k[A]2 2nd [A ] = k[A]2

order wrt A
t

A+B
products

Rate = k[A][B]
1st order wrt to
[A ]
[B]

=
= k[A][B]
A and B, 2nd
t
t
order overall

1
1
=k t+
[A]
[A]0

[A]0
2k

ln2
=
k

t1 =
2

1
k[A ]0

Factors That Affect Reaction Rates

1.
2.
3.
4.

The nature of the reactants.

The concentration of the reactants.
The temperature of the reaction.
The presence of a catalyst.

These factors are addressed in two Rate Theories:

Collision Theory of Reaction Rates

Transition State Theory

Collision Theory of Reaction Rates

Three basic events must happen for a reaction to

occur. The atoms, molecules or ions involved must:
1. Collide.
2. Collide with enough energy to break and form bonds.
3. Collide with the proper orientation for a reaction to
occur.

Transition State Theory

Postulates that reactants form a high energy intermediate, the

transition state, which then falls apart into the products.

For a reaction to occur, the reactants must acquire sufficient

energy to form the transition state.
This energy is called the activation energy or Ea.

Dependence of Rate on Temperature

Arrhenius Equation
k = Ae

Ea

Ea
ln k = ln A RT

RT

k rate constant
A frequency factor

y = mx + b form

E a Activation energy
R gas constant 8.314
T Temperature in K

Joule
mole - K

k 2 Ea 1 1
k 2 E a T2 - T1
or ln

ln
=
=
k1 R T1 T2
k1 R T2T1
2 point data form (2 Temps and
2 rate constants)

Molecularity of Reactions Reaction Mechanisms

 The mechanism proposed should be simple and consistent with
the overall reaction
-Each step in the proposed mechanism is called an ELEMENTARY STEP
or ELEMENTARY reaction
- For each elementary step, the rate law is based on the reactants
present and the order is the same as the actual stoichiometric
coefficient as shown in the reaction

General Rules in writing the rate law from a

proposed mechanism
1. Given the elementary reaction:
8

nA + mB xC + yD
Rate law based
on product
formation

1 d[C]
1 d[D]
=
= +k A
x dt
y dt

Rate law based

on reactant
consumption

1 d[A]
1 d[B]
=
= k A
n dt
m dt

General Rules in writing the rate law from a

proposed mechanism
2. Given the elementary reaction following an equilibrium
condition:
DE

nA + mB

xC + yD
DFE

Rate law
based on
product
formation

1 d[C]
1 d[D]
=
= GH A
x dt
y dt

Rate law
based on
reactant
consumpti
on

1 d[A]
1 d[B]
=
= k A
n dt
m dt

+ GH I

+ GH I

Simplifying Rate Mechanisms involving equilibrium steps:

Steady-State condition
DE

A + B

intermediate

fast

DFE

intermediate

8P

slow

Intermediate forms, but concentration is small and remains

constant

[Intermediate] does not change with time.
% M C%M

%

=0

 Steady State conditions

d intermediate
=0
dt
Non steady state conditions
If equilibrium condition is present in mechanism
Rate forward rxn = Rate of reverse rxn
Rate of product formation/reactant consumption =
Rate of product consumption/reactant formation
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