Thermochemistry Page 1

Key Terms and Concepts Heat Capacity and Specific Heat

One important thing you want to keep in mind in Some materials take more heat to increase their temperatures than others. This is because of the
higher E heat capacity (C) which is the quantity of heat required to change their temperature by 1 °C.
thermochemistry is that every system tends to go to a lower
energy state. Remember this by the example of this rock: Specific heat capacity (Cs) - the amount of heat required to raise the temperature of 1 gram
So, what is a system? In chemistry, the system is the reaction, and of the substance by 1 °C. (C or S are often used instead of Cs for specific heat capacity).
lower E
the surroundings are everything else. Molar heat capacity, the amount of heat required to raise the temperature of 1 mole
The internal energy (E) of a system is the sum of all of its kinetic and potential energy. of a substance by 1 °C.
It can be changed by work or/and heat: E = q + w Specific heat capacity of a substance, the heat absorbed by it, and the corresponding
The +/- sign of heat, work, and enthalpy depends on whether they temperature change relate as:
Mass (g)
go to the system (reaction) or from it. Temperature change (°C)
Heat (J) q = m x Cs x T
Work done on the system; +w (increases the E)
Work done by the system; -w (decreases the E) Specific heat capacity (J/g °C)

Exothermic - reaction/process evolves/releases heat (-q). For solving problems related to this equation, remember that qlost = -qgained which implies that
Endothermic - reaction/process absorbs heat (+q). amount of heat released by one object is equal to that of absorbed by the other object,

In chemical systems E is the difference in internal energy between Example: How much heat does it take to increase the temperature of a 540.6-g sample of iron
the products and the reactants: E = Eproducts - Ereactants from 20.0 °C to 84.3 °C? The specific heat of iron = 0.450 J/g °C.

State function - a property that depends only on the present state of the system, not on how the q=mxCx T
system arrived at that state. Examples: mass, volume, pressure, altitude, energy, enthalpy and etc.
Work and heat, however, are not state functions. Example: What is the final temperature when a 40 g sample of water at 90 °C is mixed with a
60 g sample at 25 °C?
Enthalpy
Remember, qlost = -qgained, so qlost + qgained = 0
Enthalpy (H) is the E plus the product of the pressure and volume of the system: H = E + PV
so, m1C Tf - T1) + m2C Tf - T2) = 0
The enthalpy change for a chemical reaction is given by the equation: Hrxn = Hproducts - Hreactants
40 g x C x (Tf – 90) + 60 g x C x (Tf – 25) = 0, Tf = 51 °C
The change in enthalpy ( H) equals the heat at constant pressure because:

H = E + PV = (qp + w) + P V = qp + w - w H = qp Calorimetry
Most reactions are carried out under constant pressure, and therefore, enthalpy change is the heat Calorimeter is the device for measuring heat flow. For many reactions, P is constant, and

released or absorbed by the reaction. therefore, qrxn = Hrxn, so the enthalpy of reaction can be determined.

The H is written in the right side of the chemical equation. The heat transfer between the reaction and the calorimeter is measured by its temperature change
and the heat capacity. qcal = Ccal x T
2 H2(g) + O2(g) 2 H2O(g) H = -484 kJ (exothermic)
qcal = -qrxn because the heat flow occur only between the reaction and the calorimeter.
This equation reads as; reacting 2 mol H2 produces 484 kJ, 1 mol O2 produces 484, and
Bomb calorimeter is an equipment that measures E for combustion reactions in a sealed
formation of 2 mol H2O produces 484 kJ of heat.
container which ensures a constant volume. And since V = constant, Erxn = qrxn.
- H indicates an exothermic reaction; heat released.
+ H indicates an endothermic reaction, heat absorbed. Most of the times, Erxn and Hrxn are approximately equal, but pay attention to what the
problem asks to determine.
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 Thermochemistry Page 2
Solving Calorimetry Problems Chemical Equations and Hrxn
Example: Calculate the energy of combustion for one mole of butane (C4H10) if burning a The Hrxn value corresponds to the given moles/coefficients of reactants and products, so if the
0.367 g sample of butane has increased the temperature of a bomb calorimeter by 7.73 °C. equation is multiplied by a factor, then Hrxn must be multiplied by the same factor:
C (C4H10) = 2.36 kJ/ °C.
2CH3OH(l) + 3O2(g) 4H2O(l) + 2CO2(g) H° = -1453 kJ
qcal = Ccal x T = 2.36 kJ/ °C x 7.73 °C = 18.2 kJ. Therefore, qrxn = E = -18.2 kJ x2 x2
4CH3OH(l) + 6O2(g) 8H2O(l) + 4CO2(g) H° = -2906 kJ
Calculate the moles of butane: n (C4H10) = 0.367 g/58.0 g/mol = 0.00633 mol

This means that 18.2 kJ heat was released when 0.00633 mol butane was burned. To get Hrxn changes the sign when a chemical equation is reversed:
the E of the reaction per mole of butane, we divide the heat of the reaction by the number
CH4(g) + 3Cl2(g) CHCl3(l) + 3HCl(g) H° = -334 kJ
of moles of butane:
Erxn = 18.2 kJ/0.00633 mol = 2.88 x 103 kJ/mol CHCl3(l) + 3HCl(g) CH4(g) + 3Cl2(g) H° = +334 kJ

Standard Enthalpies Hess’s Law

o
Standard Enthalpy Change ( H ) is when all reactants and products are in their standard states. Because enthalpy is a state function, Hrxn is the same whether the reaction takes place in
Standard states are defined as follows. one step or in a series of steps.
C
Gases: It is the pure gas at a pressure of exactly 1 atm.
Liquids and Solids: It is the pure substance in its most stable form at a H°
+50
o
2A + B C H° = +50 kJ H°
pressure of 1 atm and at the temperature of interest (usually at 25 C). 2A + B
+ -80
A Substance in Solution: It is when the concentration is exactly 1 M. C 2D H° = -80 kJ H° -30
D
o 2A + B 2D H° = -30 kJ Does not matter how 2A + B goes to D
The Standard Enthalpy of Formation ( H f) of a substance is the enthalpy change when
1 mole of the substance is formed from its constituent elements in their standard states.
Example: Use the given data for reactions 1 and 2, calculate Ho for the reaction:
For a pure element (Na, Se, O2) in its standard state, Hof = 0.
2NO2 + Cl2(g) 2NOCl(g) + O2(g), Ho = ?
Enthalpy of Reaction from Standard Enthalpies
1) 2NO(g) + Cl2(g) 2NOCl(g), Ho = -76 kJ
The standard enthalpies of formation can be found in the end of a textbook.
2) 2NO(g) + O2(g) 2NO2(g), Ho = -114 kJ
To calculate Hof, subtract the standard enthalpies of formation of the reactants from the sum of
the standard enthalpies of formation of the products, all multiplied by their coefficients.
Reverse the second reaction to make NO2 a reactant like in the target reaction. Make sure to
np - coefficients of products change the sign for Ho:
nr - coefficients of reactants
2a) 2NO2(g) 2NO(g) + O2(g), Ho = +114 kJ
Example: Calculate the heat of reaction for the combustion of ammonia:
And now, we can add equations 1 and 2a. Check if after canceling the same molecules on
4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g), H°rxn = ? both side of the equation, the target reaction is obtained with the same coefficients.

2NO(g) + Cl2(g) + 2NO2(g) 2NOCl(g) + 2NO(g) + O2(g)

Hf° for NH3(g) = – 46.2 kJ/mol, for NO(g) = 90.4 kJ/mol, for H2O(g) = – 241.8 kJ/mol

H°rxn = [4 x Hf° (NO) + 6 x Hf° (H2O)] – [4 x Hf° (NH3) + 5 x Hf° (O2)] 2NO2 + Cl2(g) 2NOCl(g) + O2(g), Ho = -76 kJ + 114 kJ = 38 kJ

H°rxn = [4 x 90.4 kJ + 6 x (–241.8)] – [4 x (–46.2 kJ) + 5 x 0] = -904.4 kJ

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