Measuring the Enthalpy Change
In an elementary laboratory, enthalpy changes are often measured in a “coffee-cup calorimeter” such as that shown in Fig. 1. Suppose the reaction to be measured is between two solutions. One of these solutions is introduced into the coffee cup, and the temperatureA physical property that indicates whether one object can transfer thermal energy to another object. of both solutions is measured.
The second solution is now introduced, the mixtureA combination of two or more substances in which the substances retain their chemical identity. stirred, and the rise in temperature recorded. Since the cup is made of polystyrene foam, a very good insulator, very little heatEnergy transferred as a result of a temperature difference; a form of energy stored in the movement of atomic-sized particles. energy escapes. It may be measurable, however, and may be represented by the calorimeter constant.
A simple experiment can be used to determine how much energy is lost to the calorimeter, the thermometer, and the surroundings. This energy loss, divided by the temperature change in the calorimeter that caused it, is often called the "calorimeter heat capacityThe quantity of heat energy transfer needed to raise the temperature of a sample of matter by one unit." or "calorimeter constant" as illustrated by the following example:
Example 1: A styrofoam cup calorimeter contains 50 mL (50.00 g) of water at 22.00°C, and 40.00 mL (42.00 g) of water at 32.00°C is added. The mixture reaches a maximum temperature of 27.30°C. What is the calorimeter constant?
Solution The hot water loses a quantity of heat qhot;
- qhot = C m ΔT = 4.18 J/g°C × 50.0 g × (27.30°C - 32.00°C) = -982 J
The cold water gains a quantity of heat qcold;
- qcold = C m ΔT = 4.18 J/g°C × 40.0 g × (27.30°C - 22.00°C) = 886 J
If no heat were lost to the surroundings,qhot would equal - qcold and their sum would be zero. But it appears that more heat was lost by the hot water than was gained by the cold. The missing heat was absorbed by the calorimeter and surroundings:
- qcal = qhot + qcold = 96 J.
The calorimeter heat capacity is this heat divided by the temperature change of the calorimeter:
Ccal = q/ΔT = 96 J / 5.3 °C = 18.1 J/°C
Using the Calorimeter Constant
The heat absorbed by the calorimeter and its contents is equal to the heat released by a chemical reactionA process in which one or more substances, the reactant or reactants, change into one or more different substances, the products; chemical change involves rearrangement, combination, or separation of atoms. Also called chemical change., as illustrated by the following example:
Example 2: The calorimeter above contains 250.0 cm3 of 1.000 M HCl (D = 1.02 g/cm3) at 20.38°C and to this is added, with stirring,250.0 cm3 of 1.000 M NaOH (D = 1.04 g/cm3) also at 20.38°C. The temperature of the mixture rises to 27.80°C. Assuming that the specific heat capacityThe quantity of heat energy transfer into a system required to raise the temperature of one gram of a substance by 1 K ( 1 °C). More correctly called specific heat capacity. of the NaCl solution that results is 4.20J/g°C, calculate ΔH, for the reaction
H3O+(aq) + OH–(aq) → 2H2O(l)
The heat change for the solution is
- qsolution = C m ΔT = 4.20 J/g°C × (250.0 × 1.02 + 250 × 1.04) g × (27.80°C - 20.38°C) = 16 049 J
The heat change for the calorimeter is
- qcalorimeter = CcalΔT = 18.1 J/°C × 7.42°C = 134 J
The total heat change of the surroundings is
- qtotal = qsolution + qcalorimeter = 16 183 J or 16.2 kJ
The heat change by the system is therefore
- qsystem = -qsurroundings = -16 183 J or -16.2 kJ
To calculate ΔH, we need to divide the enthalpy change by the amount of productA substance produced by a chemical reaction., in moles. Since 250 mL of 1 M solutions of each reactantA substance consumed by a chemical reaction. are mixed and they are in a 1:1 stoichiometric ratio, we will produce 0.250 mol (n = C × V mol = 0.250 L x 1.00 mol/L) of product, so:
This value is slightly different from the accepted value (58.7 kJ/mol) because of inaccuracies in the heat capacity of the solution and crudeness of the method.
In order to find the quantity of heat energy evolved, we need to know the rise in temperature but also the heat capacity of the calorimeter contents and calorimeter. These can be combined, and determined in a separate experiment: After the final solution has cooled to room temperature, it can be reheated to the higher temperature by means of an electrical coil. The heat supplied in this second experiment can be calculated in the usual way from the applied potential, the current flowing, and the time.
EXAMPLE 3 1.000 M HCl (250.0 cm3) at 20.38°C and 250.0 cm3 of 1.000 M NaOH also at 20.38°C are mixed in a coffee-cup calorimeter similar to that shown in the Figure. The temperature of the mixture rises to 27. 80°C. The mixture is then cooled to 20.45°C after which 24.06 V is applied to the heating coil, allowing 2.13 A to flow for 300.0 s. The temperature rises to 28.23°C. Find ΔH, for the reaction
H3O+(aq) + OH–(aq) → 2H2O(l)
Solution We first calculate the heat capacity of the contents of the calorimeter. The heat supplied by the coil qcoil is given by
q2 = 24.06 V × 2.13 A × 300.0 s = 15 374 J
Knowing the heat capacity, we can now calculate qcontents, the heat change in the contents of the experiment:
where the sign is positive since the contents have gained energy.
The system (the chemical reactants) released the same amount of energy, so it is
qsystem = - qcontents = -14.66 kJ
The reaction was exothermicDescribes a process in which energy is transferred to the surroundings as a result of a temperature difference..
Because the change occurs at constant pressureForce per unit area; in gases arising from the force exerted by collisions of gas molecules with the wall of the container., we can equate qsystem to the enthalpy change ΔH. However, the question asks for the enthalpy change per mole of acidIn Arrhenius theory, a substance that produces hydrogen ions (hydronium ions) in aqueous solution. In Bronsted-Lowry theory, a hydrogen-ion (proton) donor. In Lewis theory, a species that accepts a pair of electrons to form a covalent bond. (that is, ΔHm), while only 250 cm3 × 1 mol dm–3 = 0.250 mol acid was used. Accordingly,
Constant Volume ("Bomb") Calorimetry
Even though most chemical reactions are more conveniently studied at constant pressure than at constant volume, there are some reactions for which the opposite is true. When one of the reactants is a gasA state of matter in which a substance occupies the full volume of its container and changes shape to match the shape of the container. In a gas the distance between particles is much greater than the diameters of the particles themselves; hence the distances between particles can change as necessary so that the matter uniformly occupies its container., for instance, the reaction is much easier to carry out in a closed container called a bomb calorimeter. If a reaction is measured at constant volume, of course, we find ΔU rather than ΔH. However, almost all thermochemical data are recorded in terms of the enthalpy rather than the internal energy. It is therefore often necessary to convert a measured ΔU value to a ΔH value. This is done as shown in the following example:
EXAMPLE 4 Use the data in Table 1 in the Internal Energy section to find ΔH for the reaction
2O3(g) → 3O2(g) 25°C, 1 bar
Solution ΔH for a constant-pressure change is given by
Since ΔU is known from Table 1 in the Internal Energy section, we need only calculate P ΔV. The initial volume of the system V1 is that of 2 mol O3 at 25°C.
Similarly, the final volume is that of 3 mol O2 at 25°C:
Thus ΔH = ΔU + P ΔV = − 287.9 kJ + 2.5 kJ = − 285.5 kJ
ΔH vs. ΔU
Perhaps because values of ΔH are usually easier to measure than values of ΔU, chemists have chosen to concentrate exclusively on ΔH rather than on ΔU as a way of recording thermochemical data. Though enthalpies of formation are easy to find, equivalent tables of internal energies are nonexistent. In many ways this insistence on ΔH rather than on ΔU is a pity. In particular, it suggests that somehow the enthalpy H has more fundamental significance on the molecular level than the internal energy U. It is important to realize that this is not the case. It is the internal energy which has a simple molecular interpretation, namely, the total energy of all the molecules in the system. By contrast the enthalpy includes not only the total energy of the molecules in the system but the potential energy of the atmosphereA unit of pressure equal to 101.325 kPa or 760 mmHg; abbreviated atm. Also, the mixture of gases surrounding the earth. outside the system as well. We use the enthalpy so often because of its convenience rather than because of its molecular significance.A further point worth making about the enthalpy is that the difference between ΔH and ΔU is not often of great chemical importance. This is particularly true of reactions which involve only gases, such as the decomposition of ozone. In a gaseous reaction the main factor determining both ΔU and ΔH is the change in electronic energy. Changes in molecular energy and also the expansion workA mechanical process in which energy is transferred to or from an object, changing the state of motion of the object. P ΔV are usually small compared with this change. In the decomposition of ozone, for example, the change in electronic energy is – 290.7 kJ per 2 mol ozone. The value of ΔU is –287.9 kJ, while that of ΔH is –285.4 kJ. The three quantities are all within a few percent of each other. For many purposes, differences of this order of magnitude are immaterial. When this is the case, we can equate both ΔU and ΔH to the change in electronic energy.