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CHEMICAL THERMODYNAMICS

and THERMOCHEMISTRY
THERMODYNAMICS
the study of the changes in
energy and transfers of energy
that accompany chemical and
physical processes.

We need to address 3 fundamental
questions.

1. Will two (or more) substances react when
they are mixed under specified conditions?
2. If they do react, what energy changes and
transfers are associated with their
reaction?
3. If a reaction occurs, to what extent does it
occur?

THERMODYNAMICS
SYSTEMS and SURROUNDINGS
Transfer of Energy
Heat - q

... occurs by conduction, convection, or
radiation.
... causes a substance's temperature to
change
... is positive if thermal energy flows into
the system
... is negative if thermal energy flows out of
the system
- joules
-------------------------------------------------------
improper: "heat flow" is redundant
WORK - w
W is negative if work is done by system.
Air does work on the environment: W < 0.

W is positive if work is done on the system.

Hand does work (squeezing) on the balloon: W > 0
(Alternative: system does negative work because
force by air pressure on thumb is opposite to the
direction of motion of the thumb.)

Heat > 0
Work > 0
Heat < 0
Work < 0
INTERNAL ENERGY
Internal Energy U:
(measured in joules)

Sum of random
translational,
rotational,
and vibrational
kinetic energies
U: change in U
U > 0 is a gain of
internal energy
U < 0 is a loss of
internal energy







Vibrational kinetic
energy in solids The
hotter the object,
the larger the
vibrational kinetic
energy









Motions of a diatomic
molecule in a fluid
Law of Conservation of ENERGY
1st 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)."

For thermodynamic systems, the 1st Law is:

U = q + w
Changes in Internal energy
Example: If 1200 joules of heat are added to a
system and the system does 800 joules of work on
the surroundings, what is the :
1. energy change for the system, AE
sys
?





2. energy change of the surroundings, AE
surr
?
Thermodynamic state - set of conditions that specify
all of the properties of the system

Thermodynamic states include:
The number of moles and identity of each substance.
The physical states of each substance.
The temperature of the system.
The pressure of the system.
Thermodynamic Terms
Thermodynamic Processes
Greek isos: equal
baros: weight
adiabatos: not passable
-----------------------------------------------------

Isothermal: Same temperature
Isobaric: Same pressure
Isochoric: Same volume
Adiabatic: Zero heat flow (Q = 0)



More Thermodynamic Terms
State functions - properties of a system that depend only on
the state (Initial and Final states)
State functions are always written using capital letters.
State functions are independent of pathway.
An analog to a state function is the energy required to climb a
mountain taking two different paths.
E
1
= energy at the bottom of the mountain
E
1
= mgh
1
E
2
= energy at the top of the mountain
E
2
= mgh
2

AE = E
2
-E
1
= mgh
2
mgh
1
= mg(Ah)


Some examples of state functions are:
T, P, V, AE, AH, AG, and S
Examples of non-state functions are:
n, q, w
More Thermodynamic Terms
In thermodynamics we are often interested in changes in
functions (state functions).
We will define the change of any function X as:
AX = X
final
X
initial
If X increases AX > 0
If X decreases AX < 0.

Energy Profiles
Exothermic
reactions generate
specific amounts of
heat.

Energy of products
< energy of
reactants

Energy Profile
Endothermic
reactions
require
absorption of
energy for
complete
formation into
products

Energy of
products >
energy of
reactants
ENTHALPY, H
The enthalpy change, AH, is the change in heat
content at constant pressure.
AH = q
p

Most commonly employed energy measure for
chemical reactions since most reactions analyzed
occur at constant atmospheric pressure.

ENTHALPY of REACTIONS

AH
rxn
is the heat of reaction.
If AH
rxn
< 0 the reaction is exothermic.
If AH
rxn
> 0 the reaction is endothermic.

AH
rxn
= H
products
- H
reactants
AH
rxn
= H
substances

produced
- H
substances

consumed
AH
rxn
= H
final state
H
initial state
Thermochemical Equations and
Enthalpy of Reactions



The stoichiometric coefficients in thermochemical
equations must be interpreted as numbers of moles of
each component.

1 mol of C
5
H
12
reacts with 8 mol of O
2
to produce 5 mol of
CO
2
, 6 mol of H
2
O, and releasing 3523 kJ is referred to as
one mole of reactions.

moles 6 moles 5 moles 8 mole 1
kJ 3523 O H 6 CO 5 O 8 H C
) ( 2 2(g) 2(g) ) 12( 5
+ + +

This is an equivalent method of writing thermochemical
equations.
kJ/mol 3523 - H O H 6 CO 5 O 8 H C
o
rxn ) ( 2 2(g) 2(g) ) 12( 5
= A + +

Thermochemical Equations
N
2(g)
+ 2O
2(g)
2NO
2(g)
H
o
rxn
= 15.6 kcal/mol
N
2(g)
+ 2O
2(g)
+ 15.6 kcal 2NO
2(g)

Thermochemical Standard States
Thermochemical standard state conditions
Standard T = 298.15 K.
Standard P = 1.0000 atm.
Be careful not to confuse these values with STP.

Thermochemical standard states of matter
Standard state of pure matter the pure liquid or solid form.
Gases 1.00 atm of pressure.
For gaseous mixtures - partial pressure =1.00 atm.
Aqueous solutions 1.00 M concentration.
H
o
rxn

Standard Molar Enthalpies of
Formation, AH
f
o
Standard molar enthalpy of formation - enthalpy for
the reaction in which one mole of a substance is
formed from its constituent elements.
AH
f
o
kJ/(mole of substance assigned)

The standard molar enthalpy of formation for
MgCl
2(s)
is:
Standard Molar Enthalpies of
Formation, AH
f
o
Standard molar enthalpies of formation have been
determined for many substances and are tabulated
in Appendix K (Whitten et al, 8
th
ed).

Standard molar enthalpy of elements in their most
stable forms at 298.15 K and 1.000 atm is zero.
Reference state for all enthalpy calculations are the
constituent elements of the compound.


AH
f
o
of elements in their standard states: Zero
value

Elements AH
f
o
kJ/mole
Ca
(s)
0
C
(s)
(graphite) 0
H
+
(aq)

0
Br
2(l)
0
I
2(s)
0
S
?(?)
0
Hg
(?)
0
AH
f
o
of all compounds, ions and elements in
their non-standard states: Nonzero value







Compound AH
f
o
kJ/mole
CaF
2(s)
-1219.6
C
(s)
(diamond) +1.895
HNO
3(aq)

-207.36
HNO
3(l)
-205.0
H
2
O
(g)
-241.82
H
2
O
(l)
-285.83
Au
(g)
+366.1
Cu
2+
(aq)
+64.77
Standard Molar Enthalpies of
Formation, AH
f
o
Example: The standard molar enthalpy of formation for
phosphoric acid is -1281 kJ/mol. Write the equation for the
reaction for which AH
o
rxn
= -1281 kJ/mol.

P in standard state is P
4

Phosphoric acid in standard state is H
3
PO
4(s)

Using Enthalpies of Formation
For any process (can be reactions, physical
changes, or transformations)
xA + yB nC + mD

H
process
=
(coefficientsH
fproducts
)

(coefficientsH
freactants
)

H
process
= (nH
fC
+ mH
fD
) (xH
fA
+ yH
fB
)

Set-up the equation for Enthalpy of Reaction in:
2H
2(g)
+ O
2(g)
2H
2
O
(l)
at 25
o
C
H
rxn
o
= (2 H
f, H2O(l)
o
) (2 H
f, H2(g)
o
+ H
f, O2(g)
o

)


Using Enthalpies of Formation
Set-up the equation for Enthalpy of Vaporization in:
H
2
O
(l)
H
2
O
(g)
at 25
o
C
H
vap
o
= (1 H
f, H2O(g)
o
) (1 H
f, H2O(l)
o
)


Set-up the equation for Enthalpy of Dissolution in:
NaCl
(s)
Na
+
(aq)
+ Cl
-
(aq)

H
diss
o
= (H
f, Na+(aq)
o
+ H
f, Cl-(aq)
o
) (H
f, NaCl(s)
o
)


If the problem asks for the amount of heat
involved (either released or absorbed) in the
process:

heat of process = H
process
moles of limiting
reagent
Using Enthalpies
moles means
stoichiometry
yeah! :D
( ) mole) ( n x H q
LR mole
kJ
process
A =
Example 1: Calculate the enthalpy change for the
reaction of one mole of H
2(g)
with one mole of F
2(g)
to
form two moles of HF
(g)
at 25
o
C and one atmosphere.
o
HF(g) f
o
g) ( H f
o
) g ( F f
o
HF(g) f rxn
H 2
) H H ( - ) H 2 ( H
2 2
A =
A + A A = A
reaction of kJ/mole 542
HF mole
kJ 271
reaction of mole
HF mole 2
H
HF kJ/mole 271 H book, of K Appendix From
rxn
o
HF(g) f
=
|
.
|

\
|

|
.
|

\
|
= A
= A
Example 2: Calculate the heat involved in which 15.0
g of aluminum reacts with oxygen to form Al
2
O
3
at
25
o
C and one atmosphere.

Calculate H
rxn
= (2 -1676 kJ/mol) (0 + 0)
= -3352 kJ/mole of reaction
Calculate # of moles = 15.0 g Al/ 26.98 g Al/mole Al
= 0.555967383 moles Al

Calculate Heat
= 0.555967383 moles Al x (-3352 kJ/ 4 moles Al)
= -465.9006672 kJ
= -466 kJ or 466 kilojoules heat released

Nitrogen oxide (NO) has been found to be a
key component in many biological processes.
It also can react with oxygen to give the brown
gas NO
2
. When one mole of NO reacts with
Oxygen, 57.0 kJ of heat is evolved.

a.) What is the H
rxn
?
b.) How many grams of nitrogen oxide must
react with an excess of oxygen to liberate ten
kilojoules of heat?
CALORIMETRY
Coffee-cup calorimeter -
used to measure the
amount of heat produced
(or absorbed) in a reaction
at constant P
Method to measure q
P
for
reactions in solution.
Constant-Pressure
Calorimetry is used to
measure enthalpy of
reactions.
Styrofoam-based
calorimetry in general,
measures H
Equations
For heat transfer involving homogenous systems
- PURE substances (eg. water)
q = m c T
= mass specific heat capacity
temperature change
= g ( J/g-
o
C)
o
C

For heat transfer involving heterogenous
systems (eg. entire calorimeter)
q = C
cal
T
= ( J/
o
C)
o
C




CALORIMETRY
Calculating Enthalpy of Reaction using
Calorimetry
Main Condition: No heat flows out of the
calorimeter.
hheat
heat
surroundings
system
THEREFORE:
q
system
= 0

The entire system is
ADIABATIC
Because the entire system is adiabatic:
q
system
= 0

The system is composed of the calorimeter, the
main reactant molecules (in case of reaction), and
the solvent:

q
calorimeter
+ q
reaction
+ q
water
= 0

Therefore:

(q
calorimeter
+ q
water
) = q
reaction

Heat Surroundings = - Heat System

(q
calorimeter
+ q
water
) = q
reaction


q
calorimeter
= C
cal
T
q
water
= m
H2O
c
H2O
T
q
reaction
= H
o
reaction
x n
LR
(C
cal
T + m
H2O
c
H2O
T) = -(H
o
reaction
x n
LR
)

reaction
LR
O H O H cal
H
n
) c m T(C
2 2
A =
+ A

REMEMBER:
For reactions:
H
o
reaction
is negative: EXOTHERMIC,
T is + (T
final
> T
initial
), Increase temperature



H
o
reaction
is positive: ENDOTHERMIC,
T is - (T
final
< T
initial
), Decrease temperature


Example: A coffee-cup calorimeter is used to determine
the heat of reaction for the acid-base neutralization
CH
3
COOH
(aq)
+ NaOH
(aq)
NaCH
3
COO
(aq)
+ H
2
O
()

When we add 25.00 mL of 0.500 M NaOH at 23.000
o
C
to 25.00 mL of 0.600 M CH
3
COOH already in the
calorimeter at the same temperature, the resulting
temperature is observed to be 25.947
o
C. The heat
capacity of the empty calorimeter has previously been
determined to be 27.8 J/
0
C. Assume that the specific
heat of the mixture is the same as that of water, 4.18
J/g
0
C and that the density of the mixture is 1.02 g/mL.
Determine the Heat of Reaction for this process.
Instead of reaction, a specific amount of heat is added (or
removed) in the calorimeter (example, when a hot metal bar
or ice cubes is placed in a pail of water):

(q
cal
+ q
water
) = - q
involved


For direct heat transfer:
heat is negative if it is ADDED to the calorimeter from a source
heat is positive if it is REMOVED from the calorimeter by a source


When 3.425 kJ of heat is added to a
calorimeter containing 50.00 g of water
the temperature rises from 24.00
o
C to
36.54
o
C. Calculate the heat capacity of
the calorimeter in J/
o
C. The specific heat
of water is 4.184 J/g
o
C.
Hesss Law
Hesss Law of Heat Summation
- if a particular reaction is carried out in a series of steps,
the H for the reaction is equal to the SUM of enthalpy
changes of each step.
Hesss Law is true because AH is a state function.

| |
| | kJ 1648 H O Fe 2 O 3 Fe 4 2
kJ 4 54 H FeO 2 O Fe 2 1
o
3(s) 2 2(g) (s)
o
(g) 2(g) (s)
= A +
= A +
(s)
3 2 2(g) (s)
O Fe O FeO +
Given the following enthalpies of formation:
Determine the H
rxn
for :
Balance the reaction first!



Arrange reactions [1] and [2] so that they also have FeO and O
2
as
reactants and Fe
2
O
3
as a product.
Each reaction can be doubled, tripled, or multiplied by half, etc.
The AH
o
values are also doubled, tripled, halved, etc.
If a reaction is reversed the sign of the AH
o
is changed.
(s)
3 2 2(g) (s)
O Fe 2 O 4FeO +
For [1]: reverse,
multiply by 2
For [2]: retain
kJ/mole) 8 108 H 2O 4Fe 4FeO 2[-1]
kJ/mole) 4 54 ( 2 H ) O Fe 2 FeO 2 ( 2 2[-1]
o
2(g) (g) (s)
o
2(g) (g) (s)
+ = A +
+ = A +
| | kJ 1648 H O 2Fe 3O 4Fe 2
o
3(s) 2 2(g) (s)
= A +
kJ/mole -568 H O Fe 2 O 4FeO
rxn
(s)
3 2 2(g) (s)
= A +
Hesss Law
Example: Given the following equations and
AH
o
values






calculate AH
o
for the reaction below.
( )
( )
( )
? H NO 3 NO + O N
o
g
g
2 g 2
= A
Hesss Law
To produce silicon (used in semiconductors)
from sand (SiO
2
), a reaction is used that can be
broken down into three steps:
SiO
2
(s) + 2C(s) Si(s) + 2CO(g) H = 689.9
kJ/mole
Si(s) + 2Cl
2
(g) SiCl
4
(g) H = -657
kJ/mole
SiCl
4
(g) + 2Mg(s) 2MgCl
2
(s) + Si(s) H = -625.6
kJ/mole

a) Determine the thermochemical equation for
the formation of silicon from silicon dioxide.
b) What amount of heat is needed for the
formation of one mole of silicon?
Bond Energy
Bond energy is the amount of energy required to
break the bond and separate the atoms in the gas
phase.
To break a bond always requires an absorption of energy!
Bond Energies
Table of average bond energies
Molecule Bond Energy (kJ/mol)
F
2
(F-F) 159
Cl
2
(Cl-Cl) 243
Br
2
(Br-Br) 192
O
2
(O=O) 498
N
2
(NN) 946
Hydrogen
Bond
D
(kJ/mol)
r
(pm)
H-H 432 74
H-B 389 119
H-C 411 109
H-Si 318 148
H-Ge 288 153
H-Sn 251 170
H-N 386 101
H-P 322 144
H-As 247 152
Common Bond Energies (D) and Bond Lengths (r)
Bond
D
(kJ/mol)
r
(pm)
H-O 459 96
H-S 363 134
H-Se 276 146
H-Te 238 170
H-F 565 92
H-Cl 428 127
H-Br 362 141
H-I 295 161
Bond
D
(kJ/mol)
r
(pm)
C-P 264 184
C-O 358 143
C=O 799 120
CO 1072 113
C-B 356
C-S 272 182
C=S 573 160
C-F 485 135
C-Cl 327 177
C-Br 285 194
C-I 213 214
Bond
D
(kJ/mol)
r
(pm)
C-C 346 154
C=C 602 134
CC 835 120
C-Si 318 185
C-Ge 238 195
C-Sn 192 216
C-Pb 130 230
C-N 305 147
C=N 615 129
CN 887 116
Bond Energies
In gas phase reactions, AH
o
values may be related to
bond energies of all species in the reaction.
Example: Use the bond energies to estimate the heat of
reaction at 25
o
C for the reaction below.
(g) 2 2(g) 2(g) 4(g)
O H 2 CO O 2 CH + +
] BE 4 BE [2 - ] BE 2 BE [4 H
H - O O C O O H - C
o
298
+ + = A
= =
You should know
how to draw the
structure :<
{ }kJ/mole (464)] 4 741) ( [2 - 498)] ( 2 (414) [4 H
o
298
+ + = A
kJ/mole 686 - H
o
298
= A
Bond Energies
Calculate the average N-H bond energy in
ammonia, NH
3
.
( ) ( ) ( ) H - N
o
298 g g g 3
BE 3 H H 3 + N NH = A
( ) ( )
( )
] H [ ] H 3 H [ H
o
NH f
o
H f
o
N f
o
298
g
3 g g
A A + A = A
| | | | { }
3
o
298
o
298
NH kJ/mole 1173 H
kJ/mole 11 . 46 ) 218 ( 3 ) 7 . 472 ( H
= A
+ = A
bonds H - N mol
kJ
3
3
H - N
391
NH mole
H - N mole 3
NH kJ/mole 1173
BE average = =
Relationship of AH and AE
The total amount of heat energy that a system
can provide to its surroundings at constant
temperature and pressure is given by
AH= AE + PAV
which is the relationship between AH and AE.
AH = change in enthalpy of system
AE = change in internal energy of system
PAV = work involved in the system
Internal Energy of Gas-phase
reactions
Gas-phase reactions may involve changes in
volume, and as the volume of the container
change (due to expansion or condensation of
molecules), Work is involved in the system
n
gas
=
(total moles of gaseous products) (total moles of gaseous reactants)
Internal Energy of Gas-phase
reactions
When Then Examples
1. V
2
= V
1
PAV = 0
An
gas
= 0


gas mol 2
2(g)
(g)
2
gas mol 2
(g) 2 (g)
CO H O H CO + +
3. V
2
< V
1
PAV < 0
An
gas
< 0
2. V
2
> V
1
PAV > 0
An
gas
> 0

gas mol 1
2(g) 2(aq)
gas mol 0
(aq) (s)
H ZnCl HCl 2 Zn + +

gas mol 2
3(g)
gas mol 4
2(g) 2(g)
NH 2 H 3 N +
AH= AE + P AV

For reactions with gases: AH= AE + (An
gas
)RT

But AH = q
P
(Are these two definitions compatible?)

Remember AE = q + w.
We have also defined w = -PAV .
Thus AE = q + w = q -PAV
Consequently, AH = q- PAV + PAV = q

At constant pressure AH = q
P




Relationship of H and E
enthalpy, AH: heat measured at constant pressure.

internal energy, AE: heat measured at constant volume.

How much do the AH and AE for a reaction differ?
The difference depends on the amount of work
performed by the system or the surroundings.
Relationship of H and E
Relationship of H and E
For reactions in which the volume change is
very small or equal to zero (for reactions in
which there are no gaseous reactants or
products).
Determine the difference between H and U
at 100
o
C for CO
(g)
+ O
2(g)
CO
2(g)



Chlorine trifluoride is a toxic, intensely
reactive gas. It was used in World War II to
make incendiary bombs. It reacts with
ammonia and forms nitrogen, chlorine, and
hydrogen fluoride gases. When two moles of
chlorine trifluoride reacts, 1196 kJ of heat is
evolved.
Write the thermochemical equations for the
reaction
What is the H
o
f
for ClF
3
?