CHEM 2PA3, 2004-2005

Introduction to Expt.1 & 2

A calorimeter measures the heat evolved or absorbed by a system in a chemical change, e.g. a chemical reaction. The heat evolved (or absorbed) by a chemical reaction causes the temperature of the calorimeter to rise (or fall). The magnitude of the temperature rise (or fall) depends on the quantity of heat evolved (or absorbed) in the reaction and on the knowledge of the heat capacity of the calorimeter. The latter is defined as the quantity of heat absorbed by the calorimeter necessary to raise the temperature of the calorimeter by exactly one K, hence it is always positive.

INTRODUCTION TO CALORIMETRY

The heat capacity CS of the calorimetric system is calculated as:

CS = heat absorbed by the calorimeter temperature rise produced

[1]

Since heat is a path dependent function, the heat flow depends on the details of the path followed in the change of state and is of no general interest. However, there are two particular paths in which the heat flow in a change of state is a measure of a change in a thermodynamic function. The two specified paths are those for constant volume and constant pressure processes. (a) Heat flow at constant volume, qV: By the first law

dq = dU dW
If the only work is the work of expansion, then therefore

[2]

dw = PdV = 0 (at constant volume) dqV = dU or qv = U

[3]

The heat flow at constant volume is equal to the change in total energy of the system undergoing a change of state. Bomb calorimeters used for measuring heats of combustion ate constant volume calorimeters. (b) Heat flow at constant pressure, qp: If the work involved is expansion work only, then

dqp = dU + PdV =d (U + PV)p = dH

or

[4]

qp=H

[5]

The heat flow at constant pressure is equal to the change in enthalpy of the system undergoing the change of state. It is very convenient to carry out reactions at constant (atmospheric) pressure and we will determine the enthalpy of an ionic reaction using a constant pressure calorimeter (Experiment 1).

CHEM 2PA3, 2004-2005

Introduction to Expt.1 & 2

To determine the energy change U or enthalpy change H, the reactants and products of the reaction must be at the same temperature: [Calorimeter + Reactants ]T 0 [ Calorimeter + Products ]T 0 i.e., the reactants are completely converted into products at the same temperature, T0. The calorimeter undergoes no net change. This one-step isothermal change of state is almost impossible to carry out in practice. The reaction is therefore typically carried out in two steps: Step I: The reaction is carried out adiabatically in the calorimeter. Since q=0 for this step (for the chemicals plus the calorimeter), the temperature of the products and the calorimeter at the completion of this step, T1, will in general differ from the initial temperature, T0: [Calorimeter + Reactants ]T 0 [ Calorimeter + Products ]T 1 Step II: The products and the calorimeter at T1 are returned to the initial temperature T0. To do so, if T1>T0, the energy (or enthalpy) stored in the products must be removed:
Remove heat

[Calorimeter + Reactants ]T 0

via heat flow

[ Calorimeter + Products ]T 0

Since U and H are state functions, U and H are independent of path. Therefore we have

But

UT0=UI + UII for a constant volume calorimeter HT0 = HI + HII for a constant pressure calorimeter UI = qV = 0 for a constant volume calorimeter HI=qp = 0 for a constant pressure calorimeter UT0 = UII if both steps are at constant volume HT0 = HII if both steps are at constant pressure

[6] [7] [8] [9] [10] [11]

therefore

Thus the problem reduces itself to one of measuring or calculating UII or HII in step II. If the heat capacity of the calorimeter is known, the decrease in internal energy at constant volume (using U=CV T):

UII=(CS)V(T1T0) HII = (CS)p(T1T0)

V

[12]

or at constant pressure, the decrease in enthalpy (using H=CpT): [13] assuming that (CS) or (CS)p is essentially constant over the small temperature range T0 to T1, and that the heat capacities of reactants or products are negligible compared to CS.

CHEM 2PA3, 2004-2005

Introduction to Expt.1 & 2

The heat capacity of a calorimeter is typically determined by supplying a measured amount of heat energy to the calorimeter and observing its temperature rise. There are two main methods used: (a) Passing current through a resistance coil in the calorimeter. If a current, I amperes, flows through a resistance of R ohms, for t seconds, then the electrical energy, wel, dissipated by the resistor is: wel=R I2 t (in joules) [14] Because the resistance R is the ratio of voltage V to current I according to Ohm's Law (V = RI),

wel=V I t CS = R I 2 t/(T1T0)

[15]

If the temperature rise produced by this energy is (T1T 0), then

(b) Carrying out a chemical reaction of known heat of reaction in the same calorimeter under the same conditions. This is the method that you will use in calibrating the solution calorimeter (Experiment 1) and bomb calorimeter (Experiment 2):

[16]

CS = known heat of a chemical reaction temperature rise produced

For accurate work, the heat losses from a calorimeter must be reduced to a minimum. This can be accomplished by using Dewar vessels, which are evacuated to reduce conduction and silvered to reduce heat radiation. Or an insulating adiabatic jacket can be used to prevent transfer of heat from the calorimeter to the surroundings. Stirrers are used to speed up the attainment of thermal equilibrium in the system. This mechanical work will increase the energy slightly and hence cause a slow increase in the temperature. In spite of precautions, heat losses do occur and must be corrected for. One of the best methods for correcting heat losses is to construct a thermogram (see Instructions for the 1451 calorimeter available as a pdf on the 2PA3 WebCT site). This is a graphical procedure. The temperature of a calorimeter is monitored at equal time intervals before the reaction (pre-period), during the reaction (reaction period) and after the reaction (post-period) and a temperature-time graph is constructed. First, a certain time (15-20 minutes) is allowed after assembly of the calorimeter for all parts of the system to come to a thermal equilibrium. A timer is started and the temperature of the system is monitored for 7 minutes. This establishes the initial drift line A-B. On the 8th minute, the reaction is started and the temperature is monitored for 7 minutes to establish the reaction period B-C. Temperature readings are taken past C to establish the post-reaction drift line C-D. With the aid of a ruler, the drift lines A-B and C-D can be extrapolated into the reaction period. In order to determine the corrected temperature change produced by the reaction, it is necessary to locate a point on the thermogram at which the temperature reached 63% of its total rise (or fall). This is achieved by first measuring the vertical distance R between the extrapolated 3

CHEM 2PA3, 2004-2005

Introduction to Expt.1 & 2

lines close to the middle of the reaction period and multiplying this value by 0.63. The point P which is at a vertical distance of 0.63R from the extrapolated preperiod line (A-B) must then be located. A vertical line must then be drawn through this point P to connect both extrapolated drift lines A-B and C-D. The corrected temperature Tc rise (or fall) can then be measured as the difference between the initial temperature Ti and the final temperature Tf at the points of intersection of this line with the drift lines.