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14 Thermochemistry
14 Thermochemistry
Thermochemistry
Introduction
Every chemical change is accompanied by
energy change, principally in the form of HEAT ENERGY.
i.e: The evolution or the absorption of heat Exothermic reaction: Eheat is liberated
Temperature of rxn mixture increases
ENTHALPHY CHANGES:
enthalpy of reaction, formation, combustion, solution, neutralisation, atomisation, and lattice energy
Enthalpy Changes
Entalphy = Total energy content of
reacting materials. Symbol: H
Symbol: H
H = H Products
H Re actan ts
Products
Energy H= +ve
Reactants
ENTHALPY CHANGE, H
Hrxn = HProducts - HReactants
If Hproducts > Hreactants
then H is positive
Process is ENDOTHERMIC
Products
11
ENTHALPY CHANGE, H
Hrxn = HProducts - HReactants
If Hproducts < Hreactants
then H is negative
Process is EXOTHERMIC
THERMOCHEMICAL EQUATION:
E.g.: CH4(g) + 2O2(g) CO2(g) + 2H2O(l)
H = -890 kJ mol1
Standard conditions:
25 C/ 298 K
1 atm [aq] = 1.0 mol dm3
13
14
Rule 1:
H is directly proportional to the quantity of reactants and products.
Reactants
Products H
2(Reactants) 2(Products)(H x 2)
16
E.g:
Rule 2:
H for a reaction is equal in magnitude but opposite in sign to H for the reverse reaction.
A B B A
H -(H)
18
E.g.:
Example 1:
CH4(g) + 2O2(g) CO2(g) + 2H2O(l)
H = -890 kJ mol1
2. Physical states of the reactants 3. Allotropic forms of the reactants 4. Pressure of the gaseous reactants 5. Concentration of the reactants
- T = 25C or 298 K - P = 101 kPa or 1 atm - [Reactant] = 1.0 mol dm-3 - For Allotropic reactants, the most stable
allotrope at 298 K and 1 atm is used
Entalphy change measured under standard conditions is described as Standard Entalphy change of reaction, H.
14.2
Hesss Law
25
Reactants
Energy
H2
Intermediate
H3
H1
Products
26
H2 + H3 = H1
Reactants
H2 H1
Intermediate
H3
Products
H2 + H3 = H1
27
Hf= -x kJ mol1
Hf of elements = 0
Eg:
H2 (g) H2 (g)
Na (s) Na (s)
Ne (g) Ne (g)
He (g) He (g)
30
C (s), Graphite
C (s), Diamond CH4 (g), methane
0
+1.90 74.81
+ 20.42
110.92 395.01 424.72 484.5
1268
31
33
Hf
34
Hf = -188
a) Which substance is more stable energetically, H2O2 (l) or H2O (l)? Explain. b) Find the value of the Hf of:
kJ O (l) H2mol2 1 H2O (l) + O2 (g)
36
Cl
Br
HF is a very exothermic compound. It energetically stable. increases Theissize of length ofatomsIt does not Thestrength of HX bonds increases The bond halogen HX decreases decompose easily upon heating.
37
Hf
39
rxn
41
42
43
44
Example:
Given,
C ( s) O2 ( g ) CO2 ( g ) H1 394kJmol
1 H 2 ( g ) O2 ( g ) H 2O (l ) 2 1 H 2 286 kJmol
2C (s) H 2 ( g ) C2 H 2 ( g )
2 methods:
46
Answer :
H = +226kJ
47
-394 kJ x 2 -286 kJ
+
O2 H2O
-1074kJ
Given,
C2H2 + 1300 kJ
1 2 2 O2
2CO2 + H2O
1 2
+1300 kJ
48
1 2C + H2 +
1 2 2O2
2CO2 + H2O
1 2 2O2
-1074 kJ
+1300 kJ
+ 2
2C + H2 C2H2 +226 kJ
Hence, the entalphy change for the reaction: 2C + H2 C2H2 is +226 kJ.
49
H= y
C2H2 + 2 O2
+1300 kJ -1300 kJ
1 2
2CO2+H2O
Using Hesss Law,
Hf (CO2) = 394 kJ mol1 Hf (H2O) = 286 kJ mol1 Let: Hf (C2H2) = x kJ mol1 Thermochemical equation: Given,
Solution:
Hf(kJ mol1): x 0 2(394) (286) H = Hf(products) Hf(reactants) [2(394) + (286)] [x + 0] = 1300 x = +266 kJ mol1 51
52
E.g. 1:
CH4(g) + 2O2(g) CO2(g) + 2H2O(l) Hc = -890 kJmol-1
When one mole of methane, CH4 (g) is completely burnt in excess oxygen under standard conditions, 890 kJ of heat energy is released.
Sometimes, Hc = Hf
54
55
Hc is always exothermic
Which of the following are equations for Hc? 1. CH4 (g) + 2O2(g) CO2(g) + 2H2O(l)
7. 2Fe (s) +
3 O2(g) 2
Fe2O3(s)
2H2O (l)
H2O (g) H2O (l) NO2 (g) 2NO2 (g)
58
Isomers usually have similar Hc. Chemical reactions occurs in two steps:
1. Energy is absorbed to break bonds between atoms in reactants. 2. Energy is liberated when the atoms form new bonds to form the products.
59
H
H C H
O
C + 4H + 4O
Heat is absorbed
Energy
CH4 + 2O2
60
C H H
O
C + 4H + 4O
Heat is released
Energy
CO2 + 2H261 O
Hence, Hreaction
= Total of heat change = +(Heat absorbed) (Heat released)
C + 4H + 4O Energy CH4 + 2O2
CO2 + 2H2O
62
Alkanes
Butane VS methyl propane 1-butene VS cyclobutane
64
Hc (kJmol-1)
C5H12 C4H10
C7H16 C6H14
C10H22
65
by the addition of a CH2 group. The difference in the Hc between each successive member of the series is about 650 kJ mol1. This 650 kJ mol1 corresponds to the breaking and forming of bonds when one mole of CH2 group undergoes combustion to form CO2 and H2O. CH2
3 + 2 O2
650 kJ mol1
CO2(g) + H2O(l)
66
2877
Three CC bonds and ten CH bonds
2870
Three CC bonds & ten CH bonds 67
C
C
C
C
H H H
2800
Two CC bonds, one Four CC bonds & C=C bond & eight C eight CH bonds 68 H bonds
2877
Three CC bonds and ten CH bonds
2870
Three CC bonds & ten CH bonds 69
70
C
C
C
C
H H H
2800
Two CC bonds, one Four CC bonds & C=C bond & eight C eight CH bonds 71 H bonds
moles of H2O.
72
73
Energy
4C + 8H + 12O
Energy
4C + 8H + 12O
1-butene + 6O2
cyclobutane + 6O2
Hc
Hc
4CO2 + 4H2O
74
4CO2 + 4H2O
Your turn
Which bond is stronger, the CC bond or
C=C bond?
Example:
When 0.540 g of benzoic acid is completely burnt in a bomb calorimeter, it causes the temperature of water in the calorimeter to increase by 1.38 K. The combustion of 0.148g of butan-1-ol in the same bomb calorimeter causes an increase of 0.51 K. a. Calculate the calorimeter constant (heat capacity of the calorimeter), in kJ K1. b. Calculate the standard enthalpy change of combustion of butan-1-ol.
[The standard heat combustion of benzoic acid is -3230 kJmol-1. The Mr of benzoic acid and butan-1ol are 122 and 74 respectively]
Solution:
b.
Heat liberated from the combustion of butan-1-ol = 10.36 x 0.51 = 5.2836 kJ Standard enthalpy change of combustion = 5.2836/0.002 = 2641.8 kJ mol-1
Exercise :
Quick check 14.3
14.5
Standard Molar
Hneut
CH3COOH
NH3
50.4
Strong acid - Strong base Strong acid - Strong base Weak acid - Strong base Weak acid - Weak base
Example:
Find the standard entalphy for the following reaction:
H1
Neutralisation involving Weak acids/ Weak bases Hneut for a weak acid and a strong alkali or
vice versa is lower (less negative) than
-57.3 kJ mol-1
CH3COOH
Endothermic
H+ + CH3COO
Neutralisation involving HF
Neutralisation between HF (weak acid) &
NaOH, Hneut is more negative than -57.3 kJ mol-1 (ie. -68.6 kJ mol-1)
I.e.: HF (aq)
H+ (aq) + F- (aq)
highly exothermic
Hydration energy?
Hydration of X Formation of bonding Formation of strong bonding liberates high
hydration energy.
between particle X with H2O.
Hydration of anion
+
Anion
Water
-
Hydration of cation
+ + -
Cation
+
-
Water
+
90
H H
Hydration energy?
The size of F is very small. It has an extremely high charge
density. Therefore, strong F H2O bond is formed. Formation of strong bonding liberates high hydration energy.
Example
200 cm3 of 0.50 mol dm-3 hydrochloric acid is mixed with the same volume of 0.50 mol dm-3 sodium hydroxide at the same temperature. The temperature of the mixture is raised to 3.4 K. Calculate the enthalpy of neutralisation. [Specific heat capacity of solution = 4.2 J g-1 K-1 ] Answer: -57.12 kJ mol-1
96
conditions
Energy
AB bond is broken
E.g.:
H=+1662 kJ mol-1
CH bonds. Then (1662 4) = 416 kJ is needed to break 1 (mole) of CH bonds. The average bond entalphy of the CH bond = +416 kJ mol-1
Atom (g)
Atomisation
For diatomic gaseous:
E.g.:
Na (s) Na (g)
Hat=+107 kJ mol-1
H2 (g) H (g)
Hat=+218 kJ mol-1
E.g.:
Hat= 0 kJ mol-1
Hat= 0 kJ mol-1
About Hat
5. C (s) C (g)
6. H2O(l) H2O(g)
10.H2O(l) H2(g) +
O2 (g)
M(g) + e
-(g) M
st 1
EA
E.g:
H = -72.8 kJ mol-1
H = -364.0 kJ mol-1
i.e.
-(g) M
2nd EA
+ e
2-(g) M
1. O (g) + e O- (g)
2. O- (g) + e O2- (g)
1
HEA1=-142 kJ mol-1
H EA2=+844 kJ mol-
nd 2
EA is endothermic
Repulsion
addition of 2nd electron Energy must be absorbed to overcome the repulsive forces between the 2 negatively charged particles
x+(g) A
y-(g) B
AyBx(s)
+ +
+ +
H = Lattice energy
+ + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + +
Gaseous ions
Eg:
+(g) Na
-(g) Cl
Hlat
+ (r
+ Z
x l -) + r
Z
Hlat
Compound
NaCl
(nm)
95
(nm)
181
(kJ mol-1)
-770
NaBr
NaI
95
95
196
216
-731
-684
It involves;
enthalpy of atomisation ionisation energy electron affinity lattice energy enthalpy of formation
Important formula:
Hatom(1) + Hatom(2) + Hionization + He. affinity + Hlat
H f =
Example: Draw a Born-Haber cycle for rubidium iodide, RbI(s). Hence use the data below to calculate the enthalpy change of formation of RbI(s). Hat of rubidium = +86 kJ mol-1 Hat of iodine = +107 kJ mol-1 Hlattice of rubidium iodide = -609 kJ mol-1 IE of rubidium = +402 kJ mol-1 AE of iodine = -314 kJ mol-1
-314
-609
Rb(s) + I2(g)
Hf
+86
RbI(s)
Example: Draw a Born-Haber cycle for calcium oxide. Hence use the data below to calculate the enthalpy change of formation of calcium oxide. Enthalpy change of atomisation of calcium = +177 kJ mol-1 Enthalpy change of atomisation of oxygen = +249 kJ mol-1 Lattice energy of calcium oxide = -3409 kJ mol-1 1st Ionisation energy of calcium = +592 kJ mol-1 2nd Ionisation energy of calcium = +1100 kJ mol-1 Electron Affinity of oxygen = -140 kJ mol-1 Formation of O2- = +795 kJ mol-1
Answer
-636 kJ
-1 mol
Test Yourself 16
Hhyd
n+(g) M
+ H2O
n+(aq) M
+ H2O
n-(aq) X
Cation
Water
+
Anion
Water
-
Water-ion the water-ion bonds, the bonds are H formed. The stronger O energy. more exothermic the hydration Energy is liberated.
Try these:
Match the given Hhyd with its ions:
Li+ 78
Na+ 98
K+ 133
Rb+ 149
-410
-295
-520
Try these:
Match the given Hhyd with its ions:
Ion
Na+
Mg2+
Al3+
78
98
133
-4680
-1930
Lattice (solid)
+(g) M
-(g) X
+ + + ++ ++ +
Solid lattice structure
+ water
H2=exothermic
n+(aq) M
And:
Energy
Solubility in water
Insoluble Soluble
Lattice energy Enthalpy of hydration
Compounds
Solubility of the Group II Sulphates - The solubility of the sulphates decreases down the group - Beryllium sulphate and magnesium sulphates are soluble in water - Calcium sulphate and strontium sulphate are sparingly soluble in water - Barium sulphate is insoluble in water - When a group 2 sulphate dissolves in water MSO4 (s) + water M2+(aq) + SO42-(aq)
(ii) hydration of the gaseous ions by water molecules M2+(g) + SO42- (g) + aq M2+(aq) + SO42-(aq)
But, the increasing size of the cations causes In short, decrease in solubility in Group
2 sulphate is due to the decrease of enthalpy of hydration of the metal ions considerable changes in Hhyd
Energy
Insoluble Soluble
Lattice energy Enthalpy of hydration
BeSO4
MgSO4
CaSO4
SrSO4
BaSO4
increases on going down the group The presence of covalent character causes the compounds to have higher Hlat than expected Solubility of covalent compound is determined by its polarity~ Like-dissolves-like Rule Non-polar compound dissolve in non-polar covalent solvent, naphthalene dissolves in benzene (v.d.w forces present in both comp.) Cannot dissolves in water because cannot overcome the strong attraction in water molecules
Polar compound dissolves in polar solvent Hydroxyl group (-OH), carboxylic acid
group (COOH), amine group (NH2), sulphonic acid group (SO3H) promote the solubility of the compound in water by forming H-bonding with water More hydrophilic groups, more soluble and more H- bond formed in the water Hydrophobic groups, such as alkyl groups decrease the solubilities of organic compounds
Exercise: Checkpoint 15.6 Examination Ques. 15: Objectives,Structural Questions 1,2,3,4 & 5