IB Chemistry 2013

1

Energetics notes
(Topics 5 & 15)
5.1 Exothermic and endothermic reactions
5.1.1 Define the terms exothermic reaction, endothermic reaction and standard enthalpy change
of reaction (H

) (1)
Exothermic reaction a bond-forming reaction during which heat is released
Endothermic reaction a bond-breaking reaction that requires heat to break the molecular bonds
(hence causes surrounding environment to become cooler)
Standard enthalpy change the heat energy transferred under standard conditions (101.3kPa, 298K)

5.1.2 State that combustion and neutralisation are exothermic processes (1)
Combustion and neutralisation are always exothermic processes

5.1.3 Apply the relationship between temperature change, enthalpy change and the
classification of a reaction as endothermic or exothermic (2)
Endothermic reaction:
When enthalpy of products is greater than reactants, energy is absorbed from the
surroundings (bond-breaking)
Temperature decreases
H is ve
Exothermic reaction:
When enthalpy of reactants is greater than products, energy is released (bond forming)
Temperature increases
H is +ve

5.1.4 Deduce, from an enthalpy level diagram, the relative stabilities of reactants and products,
and the sign of the enthalpy change for the reaction (3)




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5.2 Calculation of enthalpy changes
5.2.1 Calculate the heat energy change when the temperature of a pure substance is changed (2)
H = m x c x T
H = enthalpy change
m = mass of solvent + substance (g)
c
1
= specific heat capacity (usually of water 4.18J C
-1
g
-1
)
T = change in temperature (can be C or K)
5.2.2 Design suitable experimental procedures for measuring the heat energy changes of
reactions (3)
See extra notes

5.2.3 Calculate the enthalpy change for a reaction using experimental data on temperature
changes, quantities of reactants and mass of water (2)
1. Will be given a H value next to chemical equation (in kJ mol
-1
)
2. Find the no. of moles of the required substance
3. Amount of energy = H value x no. of mole of substance present
For example:

Calculate the amount of energy released when 500cm3 of methane gas at STP reacts with excess air
according to the equation

CH
4(g)
+ 2O
2(g)
CO
2(g)
+ 2H
2
O
(l)
H = 890 kJ mol
-1













Therefore, the energy released in this combustion reaction is 19.9 kJ

1
*Specific heat capacity the amount of heat energy required to raise the temperature of 1.00g of a substance by 1.00C

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5.2.4 Evaluate the results of experiments to determine enthalpy changes (3)
Consider systematic and random errors
E.g.
Heat lost to surroundings, therefore less energy released than theoretical values
(combustion reactions)
Calorimeter not calibrated properly/fully insulated
Heat absorbed by container
Therefore, calculated heat energy change is inaccurate

5.3 Hesss law
5.3.1 Determine the enthalpy change of a reaction that is the sum of two or three reactions with
known enthalpy changes (3)

H = sum (H
f(products)
) sum (H
f(reactants)
)

All elements in standard states are assigned an energy value of zero (0)
Formation of products is the sum of the enthalpies of formation of components
Example 2:
Calculate the enthalpy change in the reaction:

2KHCO3 (s) --------> K
2
CO3 (s) + CO
2
(g) + H
2
O (l)
Hess' law by manipulation of the equations...
2KHCO3 --> K
2
CO3 + CO
2
+ H
2
O
2K + H2 + 2C + 3O
2
--> 2KHCO3 H = 2(-959) = -1918
2K + C + 3/2O
2
--> K2CO3 H = -1146
SUBTRACT
H2 + C + 3/2O2 --> 2KHCO3 - K2CO3 H = -772
H2 + 1/2O2 ---> H2O H = -286
SUBTRACT
C + O2 --> 2KHCO3 - K2CO3 - H20 H = -486
C + O2 --> CO2 H = -394
SUBTRACT
ZERO ---> 2KHCO3 - K2CO3 - H20 -CO2 H = -92
REARRANGE
K2CO3 + H20 + CO2 --> 2KHCO3 H = -92
THEREFORE
2KHCO3 --> K2CO3 + H20 + CO2 H = +92


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5.4 Bond enthalpies
5.4.1 Define the term average bond enthalpy (1)
Average bond enthalpy the amount of energy required to break one mole of bonds in a gaseous
state averaged across a range of compounds containing that bond

5.4.2 Explain, in terms of average bond enthalpies, why some reactions are exothermic and
others are endothermic (3)
All bond values are positive
When bond-breaking requires more energy than bond-forming, reaction is endothermic
When more bonds forming than breaking, reaction is exothermic

15.1 Standard enthalpy changes of reaction (HL)
15.1.1 Define and apply the terms standard state, standard enthalpy change of formation (H
f

)
and standard enthalpy change of combustion (H
c

) (2)
Standard state the state at which a substance will be found at 298K and 1.01 x 10
2
kPa
Standard enthalpy change of formation (H
f

) the enthalpy change when one mole of a

compound is formed from its elements at a pressure of 1.01 x 10
2
kPa and 298K
The standard enthalpy change of formation of any element in its most table state is zero
Standard enthalpy of change of combustion (H
c

) The enthalpy change for a combustion

reaction under standard conditions
e.g. CH
4(g)
+ 2O
2(g)
CO
2(g)
+ 2H
2
O
(l)

15.1.2 Determine the enthalpy change of a reaction using standard enthalpy changes of
formation and combustion (3)

H = H(products) H(reactants)
H

rxn
= nH

f(
(products) - mH

f
(reactants)

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E.g. 1 Write the chemical equation, including state symbols, representing the standard enthalpy
of formation of nitric acid
Constituent reactants H
2
, N
2
, O
2

Product HNO
3

All states are those that occur under standard conditions
1
2
Error! Bookmark not defined.H
2(g)
+
1
2
N
2(g)
+ 1
1
2
O
2(g)
HNO
3(l)


E.g. 2 Use the information from the table to calculate the enthalpy change for the complete
combustion of ethane according to the following equation:
C
2
H
4(g)
+ 3O
2(g)
2CO
2(g)
+ 2H
2
O
(l)













H

C
= *(2 mol) H

f
(CO
2
) + (2 mol) H

f
(H
2
O)] [(1 mol) H

f
(C
2
H
4
) + (3 mol) (O
2
)]
= [(2 x -394) + (2 x -242)] [+52 + (3 x 0)]
= -788 484 52 = -1324 kJ mol
-1

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E.g. 3 Find the H

rxn
for the acid-base reaction between ammonia and hydrogen bromide using
standard enthalpy changes of formation
NH
3(g)
+ HBr
(g)
NH
4
Br
(s)

H

rxn
= n H

f
(products) m H

f
(reactants)
= 271 (-46 + 36)
= 271 (-82)
= 289 kJ mol
-1



15.2 Born-Haber cycle
15.2.1 Define and apply the terms lattice enthalpy and electron affinity (2)
Lattice enthalpy the lattice enthalpy of an ionic solid is the energy required to completely separate
one mole of a solid ionic compound into its gaseous ions
Provides a quantitative measure of the stability of an ionic solid

Electron affinity the energy change that occurs when one mole of electrons is accepted by one
mole of atoms in the gaseous state to form one mole of negative ions

15.2.2 Explain how the relative sizes and the charges of ions affect the lattice enthalpies of
different ionic compounds (3)

Lattice enthalpy (charge on cation) x (charge on ion)
sum of ionic radii


The size of the force of attraction, F, of one ion on another is given by Coulombs law:

F = k
q
1
q
2
r
2
E.g. 1 NaCl and KCl
Cations are different, but the anion stays the same
Na
+
and K
+
have the same charge, but the ionic radius of K
+
is greater, due to the extra shell
of e
-
around the K
+
ion
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Weaker attractive force between K
+
and Cl
-
than Na
+
and Cl
-

Increasing the charge on an ion increases the lattice enthalpy
Decreasing the ionic radius increases the lattice enthalpy
The smaller the ions and the larger their charge, the greater the lattice enthalpy of the ionic
compound will be

15.2.3 Construct a Born-Haber cycle for group 1 and 2 oxides and chlorides, and use it to
calculate an enthalpy change (3)
1. Atomisation of the solid metal: H

at
metal goes into the gaseous state (endothermic)
2. Ionisation of the gaseous metal: H

I
metal loses e
-
to form a cation (endothermic)
3. Dissociation or atomisation of the molecular non-metal into atoms: H

D
non-metal goes
into the gaseous state and is broken into individual atoms (endothermic process)
4. Addition of electrons to the non-metal atoms (electron affinity): H

E
non-metal atoms
gain electrons to form anions (exothermic)
5. Reaction between the gaseous ions to form the solid ionic lattice: H

lf
(exothermic)

Enthalpy of formation of the ionic compound H

lf
has the same magnitude but the
opposite sign to the lattice enthalpy of the compound, H

L



















The more negative the standard enthalpy change of formation of the ionic compound, the
more stable the compound will be
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15.2.4 Discuss the difference between theoretical and experimental lattice enthalpy values of
ionic compounds in terms of r their covalent character (3)
Theoretical assumptions:
Ions themselves are treated as point charges
Structure is purely ionic


Overall lattice enthalpy is a function of electrostatic attraction, the lattice structure and the
magnitude of the charges on the ions
Based on electrostatic attractions between ions
Experimental lattice enthalpy always greater than theoretical lattice enthalpy, indicating
extra bonding b/w ions

E.g. AgI
Ag
+
much smaller than I
-
- able to approach I
-
ion closely
Can distort its electron cloud by attracting the electrons of the iodide ion towards itself
Iodide ion easy to distort because its valence e
-
, in the 5
th
e
-
shell, are far from the nucleus
Distortion means there are more e
-
than expected b/w the silver and iodine nuclei
There is a greater degree of covalent character in AgI than NaCl described as polarised


% discrepancy =
experimental value - theoretical value
experimental value x 100



Covalent character increases down a group and across a period (stronger
electronegativity across a period and less electrostatic attraction b/w valence e
-
and
nucleus down group)


Covalent character increases as the difference between experimental and theoretical
values of lattice enthalpy increases


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15.3 Entropy
15.3.1 State and explain the factors that increase the entropy in a system (3)
Entropy measure of the randomness or disorder of a system (given a symbol of S)
2
nd
law of thermodynamics states that the entropy of an isolated system (when not in
equilibrium) will tend to increase over time.
An increase in entropy produces a positive S value

Endothermic reaction = bond breaking = increase in entropy
Exothermic reaction = bond-forming = increasing stability = decrease in entropy
Factors that contribute to the entropy of a system:
1. The no. of particles
E.g. Dissolution of ammonium nitrate
Endothermic reaction when ammonium nitrate dissolves, the ions spread throughout the
solution in a random arrangement
NH
4
NO
3(s)
NH
4
+
(aq)
+ NO
3
-
(aq)
H = +25kJ mol
-1
Two particles on the RHS for every particle on the LHS
increase in entropy

2. The state of the particles (increasing entropy: s < l < g)
E.g. Entropy increases when ice
(s)
water
(l)
water vapour
(g)

3. Nature of the particles
Decomposition of organic matter is accompanied by an increase in entropy
E.g. Decomposition of ammonium carbonate
(NH
4
)
2
CO
3(s)
2NH
3(g)
+ CO
2(g)
+ H
2
O
(g)
H = +68kJ mol
-1
1 mole decomposes to form 4 mole of gases
Increase in no. of mole of particles + change in state = increase in entropy

4. Increase in temperature
When temperature increases, kinetic energy available to particles also increases
Particles gain more freedom to move, hence increasing chances of collision
E.g. all particles have greater entropy at room temperature than at 0C
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15.3.2 Predict whether the entropy change (S) for a given reaction or process is positive or
negative (3)
E.g. 1
CH
4(g)
+ 2O
2(g)
CO
2(g)
+ 2H
2
O
(g)
3 mol of gaseous reactants and 3 mole of gaseous products
S would be 0
E.g. 2
CO
2(g)
+ 3H
2(g)
CH
3
OH
(g)
+ H
2
O
(g)
4 mol of gaseous reactants and 2 mol of gaseous products
S is ve, entropy has decreased
E.g. 3
2Al
(s)
+ 3S
(s)
Al
2
S
3(s)

5 mol of solid reactants and 1 mol of solid product
S is ve, entropy has decreased
E.g. 4
CH
4(g)
+ H
2
O
(g)
3H
2(g)
+ CO
2(g)
2 mol of gaseous reactants and 4 mol of gaseous products
S is +ve, entropy has increased


15.3.3 Calculate the standard entropy change for a reaction (S

) using standard entropy values

(S

) (2)
For a reaction:
aA + bB cC + dD
S

rxn
is given by:

S

= S

(products) S

(reactants)
= [c S

(C) + dS

(D)] [aS

(A) + bS

(B)]


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15.4 Spontaneity
15.4.1 Predict whether a reaction or process will be spontaneous by using the sign of G

(3)
Gibbs free energy, G, reflects balance between enthalpy and entropy
Described as the driving force of a chemical reaction

G = H TS

H = drive toward stability
- When H < 0 the products are more stable (lower enthalpy) than the reactants

S = drive toward disorder
- When S > 0, the products are more disordered than the reactants
- Increasing T increases influence of S on the reaction force

Temperature always quoted in Kelvin for calculations of G

Usually quoted under standard conditions (298K and 101.3kPa)

G = G(products) G(reactants)

If G

< 0 the reaction is spontaneous

If G

= 0 the reaction is at equilibrium

If G

> 0, the reaction is not spontaneous

Summary of effects of signs of H

and S

on G

Positive (+) Negative (-)
S

Positive (+) G

is ve at high temperatures
and +ve at low temperatures
e.g. H
2(g)
+ I
1(g)
2HI
(g)
G

is always ve. These reactions

are always spontaneous.
e.g. 2H
2
O
2(l)
2H
2
O
(g)
+ O
2(g)

Negative (-) G

is always +ve. These reactions

are never spontaneous
e.g. 3O
2(g)
2O
3(g)
G

is +ve at high temperatures

and ve at low temperatures.
e.g. NH
3(g)
+ HCl
(g)
NH
4
Cl
(s)
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15.4.2 Calculate G

for a reaction using the equation G

= H

- TS

and by using values of

the standard free energy change of formation G
f

(2)

G

rxn =
nG

f
(products) - mG

f
(reactants)


15.4.3 Predict the effect of a change in temperature on the spontaneity of a reaction using
standard entropy and enthalpy changes and the equation G

= H

- TS

(3)
As temperature increases, TS

becomes more negative

When this becomes greater than -92600, G

will become positive and reaction will no

longer be spontaneous



T =
H - G
S



E.g. Determine the standard Gibbs free energy of the following reaction
2C
2
H
6(g)
+ 7O
2(g)
4CO
2(g)
+ 6H
2
O
(g)

Solution:
G

rxn
= [(4 mol)(G

f
(CO
2
) + (6 mol)(G

f
(H
2
O)] [(2 mol)(G

f
(C
2
H
6
) + (7 mol)(G

f
(O
2
)]
= [(4 mol)(-394 kJ mol
-1
) + (6 mol)(-229 kJ mol
-1
)] [(2 mol)(-33 kJ mol
-1
) + (7 mol)(0 kJ mol
-1
)]
= [(-1576) + (-1374)] [-66]
= -2884 kJ mol
-1
Reaction is spontaneous under standard conditions