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Thermo Chemistry

This document discusses key concepts in thermodynamics including: 1) The first law of thermodynamics which states that the change in internal energy of a system equals the heat added plus work done. Internal energy is defined as the sum of kinetic and potential energy of particles in a system. 2) Enthalpy is the heat given off or absorbed during a chemical reaction at constant pressure. It is equal to the change in internal energy plus the product of pressure and change in volume. 3) Entropy measures the degree of disorder in a system. Reactions favor higher entropy states. 4) Gibbs free energy is a measure of the energy that drives a reaction to minimize chemical potential. It is

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82 views5 pages

Thermo Chemistry

This document discusses key concepts in thermodynamics including: 1) The first law of thermodynamics which states that the change in internal energy of a system equals the heat added plus work done. Internal energy is defined as the sum of kinetic and potential energy of particles in a system. 2) Enthalpy is the heat given off or absorbed during a chemical reaction at constant pressure. It is equal to the change in internal energy plus the product of pressure and change in volume. 3) Entropy measures the degree of disorder in a system. Reactions favor higher entropy states. 4) Gibbs free energy is a measure of the energy that drives a reaction to minimize chemical potential. It is

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roythomasc
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THERMODYNAMICS

Aims-
Internal energy
Enthalpy
Entropy
Gibbs Free Energy

First law of thermodynamics states that the change in the internal energy of a system is equal to the sum of
the heat added to the system and the work done on it.

∆𝑈 = ∆𝑄 − 𝑃∆𝑉

Usually we just apply ∆𝑄 = 𝑚𝑐∆𝑇 and 𝑊 = −𝑃∆𝑉

Internal energy is defined as the energy associated with the random, disordered motion of molecules. It is
the sum of the kinetic and potential energies of the particles that form the system.

Note that internal energy is not zero if a system is hypothetically reduced to a temperature of absolute
zero. It simply means all electrons are orbiting in their lowest (ground state) energies. There is still
chemical potential energy to consider for example.

Enthalpy

The heat given off or absorbed during a chemical reaction at constant pressure is equal to the change in
the enthalpy of the system.

Since the reaction is taking place at constant pressure, the change in the enthalpy that occurs during the
reaction is equal to the change in the internal energy of the system plus the product of the constant
pressure times the change in the volume of the system.
H = E + P∆V (at constant pressure)

Substituting the first law of thermodynamics into this equation gives the following result.

H = (qp - P∆V ) + P∆V

H = qp (at constant pressure)

We use 25⁰C and 1 atm as reference pressure denoting this ∆𝐻 𝜃

Thus
𝑐𝑜𝑚𝑏𝑢𝑠𝑡𝑖𝑜𝑛
2𝐻2 + 𝑂2 → 2𝐻2 𝑂 ∆𝐻 𝜃 = −572 𝑘𝐽/𝑚𝑜𝑙

1
1 𝑐𝑜𝑚𝑏𝑢𝑠𝑡𝑖𝑜𝑛
𝐻2 + 2𝑂2 → 𝐻2 𝑂 ∆𝐻 𝜃 = −286 𝑘𝐽/𝑚𝑜𝑙

Note that exothermic reactions have negative enthalpy changes


Note that the ‘per mole’ relates to the reagents in molar proportions

Standard molar enthalpies of combustion in pure oxygen ∆𝐻 𝜃 (kJ/mol)


hydrogen -285.8
C (graphite) -393.5
C (diamond) -395.4
methanol -726.3
methane -890.2
ethanol -1366.9
ethane -1410.9
ethane -1559.7
propane -2219.7
glucose -2816.0
butene -2878.6
benzene -3267.4

Example
𝑐𝑜𝑚𝑏𝑢𝑠𝑡𝑖𝑜𝑛
𝐶3 𝐻8 (𝑔) + 5𝑂2 (𝑔) → 3𝐶𝑂2 (𝑔) + 4𝐻2 𝑂(𝑙) ∆𝐻 𝜃 = −2219.7 𝑘𝐽/𝑚𝑜𝑙

Note there is a phase change in this equation.


If the experiment is to be ONLY gas-phase then we need to perform it above 100⁰C.
If we want to know the chemical energy without the phase change we need to distinguish enthalpy from
chemical energy.

BOND ENERGIES

kJ/mol
O-O 138
I-I 151
N-N 159
Br-Br 193
Cl-Cl 243
C-N 293
H-I 297
C-Cl 326
C-O 335
C-C 347
H-Br 364
N-H 389
C-H 413
H-Cl 431
H-H 435
O-H 464
H-F 565
2
C=C 619
CΞC 837

Example:
How much energy is released when ethane is reacted with hydrogen to produce ethane?

𝐶2 𝐻4 + 𝐻2 → 𝐶2 𝐻6

Bonds broken: C=C, H-H energy: 619+435 = 1054 consumed


Bonds formed: C-C, 2(C-H) energy: 347+2(413) = 1173 released
difference = -119 J/mol (negative meaning released)
Note: Net C-H bond change taken in calculation : 4C-H from reactants broken - 6 C-H formed in products = 2 C-H
formed

3
ENTROPY
The “degree of disorder” in a system.
o Takes more energy to make a mess
o Something organised is more-crystalline and lower energy

The equation we need for this is:


∆𝐻
∆𝑆𝑡𝑜𝑡𝑎𝑙 = ∆𝑆𝑠𝑦𝑠𝑡𝑒𝑚 −
𝑇
Reactant ∆𝑆𝑠𝑦𝑠𝑡𝑒𝑚
C (diamond) 2.4
Cu 33.1
SiO2 41.8
CuO 43.5
I2 116.8
H2O 360.2 These figures are the energy change of
Hg 69.9 the physical system that accompanies
Br2 76.0
‘typical’ reactions at STP.
C2H5OH 151.6
H2 131.0
CH4 186.2
O2 205.0
CO2 213.6
Cl2 233.0
NO2 239.9

Example:

What is the entropy change in the combustion of methane in pure oxygen?

𝑐𝑜𝑚𝑏𝑢𝑠𝑡𝑖𝑜𝑛
𝐶𝐻4 (𝑔) + 3𝑂2 (𝑔) → 𝐶𝑂2 (𝑔) + 2𝐻2 𝑂(𝑙)

𝑘𝐽
From the first page ∆𝐻 𝑂 = −890.2 𝑚𝑜𝑙 = −890200 𝐽/𝑚𝑜𝑙
Since this is at STP T = 298 K

Take figures from the table above and write them under the equation:
𝐶𝐻4 3𝑂2 𝐶𝑂2 2𝐻2 𝑂
+ → +
186.2 3(205) 213.6 2(360.2)

Find the difference of products minus reagents to get ∆𝑆𝑠𝑦𝑠𝑡𝑒𝑚 = −326.4 𝐽/𝐾/𝑚𝑜𝑙

∆𝐻
∆𝑆𝑡𝑜𝑡𝑎𝑙 = ∆𝑆𝑠𝑦𝑠𝑡𝑒𝑚 −
𝑇
−890200
becomes ∆𝑆𝑡𝑜𝑡𝑎𝑙 = −326.4 − 298
= 2660.8 J/K/mol
= 2.66 kJ/K/mol

Note that this figure is positive -> entropy always increases

Note also that the system enthalpy was negative. This is not only because gas was converted to liquid, but
also four moles gas was converted to three moles gas.

4
GIBBS FREE ENERGY

Gibbs is an attempt to separate chemical energy from entropy.


It is a measure of the energy which drives a reaction to achieve minimum chemical-potential-energy.

Here I give only a definition – the use is beyond scope of the module. See any standard chemistry book.

∆𝐺 = ∆𝐻 − 𝑇∆𝑆

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