Thermochemistry 2 PDF

Enthalpy and Calorimetry
Enthalpy, H, is the heat content of the reacting system. It reflects the number and kinds of chemical bonds
in the reactants and products. When a chemical reaction releases heat, it is said to be exothermic; the heat
content of the products is less than that of the reactants and ∆H has, by convention, a negative value.
Reacting systems that take up heat from their surroundings are endothermic and have positive values of ∆H.
So, 𝐻 = 𝐸 + 𝑃𝑉
Where E is the internal energy of the system, P is the pressure of the system, and V is the volume of the
system.
Since internal energy, pressure, and volume are all state functions, enthalpy is also a state function, consider
a process carried out at constant pressure and where the only work allowed is pressure– volume work (𝑤 =
−𝑃∆𝑉). Under these conditions, the expression is
∆E =qp + w
∆E =qp - P∆V
qp = ∆E + P∆V
Where qp is the heat at constant pressure.
Change in enthalpy is the change in internal energy of the system and change in pressure and volume work.
At constant pressure (where only PV work is allowed), the change in enthalpy ∆H of the system is equal to the
energy flow as heat. This means that for a reaction studied at constant pressure, the flow of heat is a measure
of the change in enthalpy for the system. For this reason, the terms heat of reaction and change in enthalpy are
used interchangeably for reactions studied at constant pressure.
For a chemical reaction, the enthalpy change is given by the equation
In a case in which the products of a reaction have a greater enthalpy than the reactants, ∆H will be positive.
Thus heat will be absorbed by the system, and the reaction is endothermic. On the other hand, if the enthalpy
of the products is less than that of the reactants, ∆H will be negative. In this case the overall decrease in
enthalpy is achieved by the generation of heat, and the reaction is exothermic.
Problems on Enthalpy
1. When 1 mole of methane (CH4) is burned at constant pressure, 890 kJ of energy is released as heat.
Calculate ∆H for a process in which a 5.8-g sample of methane is burned at constant pressure.
To calculate ∆H
The moles of CH4 burned
Then
Thus, when a 5.8-g sample of CH4 is burned at constant pressure,

∆H = heat flow = -320 kJ
Calorimetry
The device used experimentally to determine the heat associated with a chemical reaction is called a
calorimeter. Calorimetry, the science of measuring heat, is based on o bserving the temperature change
when a body absorbs or discharges energy as heat. Substances respond differently to being heated. One
substance might require a great deal of heat energy to raise its temperature by one degree, whereas another
will exhibit the same temperature change after absorbing relatively little heat. The heat capacity C of a
substance, which is a measure of this property,
Heat absorbed
𝑪=
Increased in temperature
When an element or a compound is heated, the energy required will depend on the amount of the substance
present. Thus, the heat capacity of a substance, the amount of substance must be specified. If the heat capacity
is given per gram of substance, it is called the specific heat capacity, and its units are J/8C ∙ g or J/K ∙ g. If the
heat capacity is given per mole of the substance, it is called the molar heat capacity, and it has the units
J/8C ∙ mol or J/K ∙ mol.
Specific heat capacity: the energy required to raise the temperature of one gram of a substance by one degree
Celsius.
Molar heat capacity: the energy required to raise the temperature of one mole of a substance by one degree
Celsius.
The calorimeters used for highly accurate work are precision instruments; a very simple calorimeter can be
used to examine the fundamentals of calorimetry. A calorimeter has two nested Styrofoam cups with a cover
through which a stirrer and thermometer can be inserted. This device is called a “coffee-cup calorimeter.” In
this the outer cup is used to provide extra insulation. The inner cup holds the solution in which the reaction
occurs. Coffee-cup calorimeter also called as Constant-pressure calorimetry and is used in determining the
changes in enthalpy (heats of reactions) for reactions occurring in solutions under these conditions, the
change in enthalpy equals the heat; that is, ∆H = qp.
If two reactants at the same temperature are mixed and the resulting solution gets warmer, this means the
reaction taking place is exothermic. An endothermic reaction cools the solution.
For example, suppose we mix 50.0 mL of 1.0 M HCl at 25.00C with 50.0 mL of 1.0 M NaOH also at 250C in a
calorimeter. After the reactants are mixed by stirring, the temperature is observed to increase to 31.90C. This
is an exothermic reaction. The quantity of energy released can be determined from the temperature increase,
the mass of solution, and the specific heat capacity of the solution. This means that 4.18 J of energy is
required to raise the temperature of 1 g of water by 10C.
From these we can calculate the heat (change in enthalpy)for the neutralization reaction:
Energy (as heat) released by the reaction
= energy (as heat) absorbed by the solution
= specific heat capacity X mass of solution X increase in temperature
= s X m X ∆T
In this case the increase in temperature (∆T ) = 31.90C - 25.00C = 6.90C, and the mass of solution (m) 5=
100.0 mL X 1.0 g/mL = 1.0 X 102 g. Thus energy released 1as heat = s X m X ∆T
Enthalpies of reaction are often expressed in terms of moles of reacting substances. The number of moles of
H+ ions consumed in the preceding experiment is of heat released per 1.0 mole of H+ ions neutralized.
Thus the magnitude of the enthalpy change per mole for the reaction is 58 kJ/mol. Since heat is evolved,
∆H = -58 kJ/mol.
To summarize, when an object changes temperature, the heat can be calculated from the equation
q= s X m X ∆T
Where s is the specific heat capacity, m is the mass, and ∆T is the change in temperature. Note that when ∆T
is positive, q also has a positive sign. The object has absorbed heat, so its temperature increases.
Problems on calorimetry
1. When 1.00 L of 1.00 M Ba(NO3)2 solution at 25.00C is mixed with 1.00 L of 1.00 M Na2SO4 solution at
25.00C in a calorimeter, the white solid BaSO4 forms, and the temperature of the mixture increases to
28.10C. Assuming that the calorimeter absorbs only a negligible quantity of heat, the specific heat capacity
of the solution is 4.18 J/0C∙ g, and the density of the final solution is 1.0 g/mL, calculate the enthalpy
change per mole of BaSO4 formed.
To calculate ∆H per mole of BaSO4 formed the given values are…
Net ionic equation for the reaction is
Then ∆H
Since the temperature increases, formation of solid BaSO4 must be exothermic; ∆H is negative.
Heat evolved by the reaction
= heat absorbed by the solution
5= specific heat capacity X mass of solution X increase in temperature
The mass of the final solution is..
The increased temperature is..
The heat evolved by the reaction is…..
Thus
To study the energy changes in reactions under conditions of constant volume, a “bomb calorimeter” is used
this works by the principle of constant-volume calorimetry. For a constant-volume process, the change in
volume ∆V is equal to zero, so work (which is -P∆V) is also equal to zero. Therefore,
To measure the energy of combustion of octane (C8H18), a component of gasoline. A 0.5269-g sample of
octane is placed in a bomb calorimeter known to have a heat capacity of 11.3 kJ/8C. This means that 11.3 kJ
of energy is required to raise the temperature of the water and other parts of the calorimeter by 10C. The
octane is ignited in the presence of excess oxygen, and the temperature increase of the calorimeter is 2.250C.
The amount of energy released is calculated as follows:
Energy released by the reaction
= temperature increase X energy required to change the temperature by 1°C
=∆T X heat capacity of calorimeter
This means that 25.4 kJ of energy was released by the combustion of 0.5269 g octane.
The number of moles of octane is
Since 25.4 kJ of energy was released for 4.614 x 10-3 mole of octane, the energy released per mole is
Since the reaction is exothermic, ∆E is negative:

∆E combustion = -5.50 x 103 kJ/mol
Note that since no work is done in this case, ∆E is equal to the heat.
∆E = q + w = q since w = 0
Thus
q = -5.50 x 103 kJ/mol.

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Enthalpy and Calorimetry

The moles of CH4 burned

Thus, when a 5.8-g sample of CH4 is burned at constant pressure,

Net ionic equation for the reaction is

The increased temperature is..

The heat evolved by the reaction is…..

Since the reaction is exothermic, ∆E is negative:

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