LEC

Determination of the hydration enthalpy of an electrolyte

02.07

Related concepts Universal power supply 13500.93 1

Integral enthalpy of solution, Hess’s law, lattice energy, ion sol- Connection cable, l = 500 mm, black 07361.05 4
vation, calorimetry. Magnetic heating stirrer 35720.93 1
Magnetic stirrer bar, l = 30 mm, oval 35680.04 1
Principle Separator for magnetic bars 35680.03 1
When a solid electrolyte dissolves in water, a positive or negative Support rod, l = 500 mm, M10 thread 02022.20 1
heat effect occurs as a result of the destruction of the crystal lat- Right angle clamp 37697.00 1
tice and the formation of hydrated ions. The enthalpy of hydra- Universal clamp 37715.00 1
tion of copper sulphate can be calculated from the different Laboratory balance
heats of reaction measured when anhydrous and hydrated cop- with data output, 800/1600/3200 g 48803.93 1
per sulphate are separately dissolved in water. Mortar with pestle, 190 ml 32604.00 1
Spoon, special steel, 33398.00 1
Tasks Porcelain dish, 115 ml, do = 100 mm 32518.00 1
1. Record temperature-time curves for the dissolution of anhy- Crucible tongs, 200 mm 33600.00 1
drous copper sulphate and hydrated copper sulphate in Tripod, d = 140 mm, h = 240 mm 33302.00 1
water. Wire gauze, 160 x 160 mm 33287.01 1
2. Calculate the hydration enthalpy of anhydrous copper(II)sul- Butane burner 32178.00 1
phate. Butane cartridge 47535.00 1
Powder funnel, do = 100 mm 34472.00 1
Glass beaker, 50 ml, tall 36001.00 1
Equipment Stop watch, digital, 1/100 s 03071.01 1
Cobra3 Basic-Unit 12150.00 1 Wash bottle, 500 ml, plastic 33931.00 1
Power supply 12 V/2 A 12151.99 1 Desiccator, 34126.00 1
Data cable, RS232 14602.00 1 Porcelain plate for desiccators 32474.00 1
Temperature measuring module Pt 100 12102.00 1 Silicone grease, 100 g 31863.10 1
Software Cobra 3 Temperature 14503.61 1 Silica gel, orange, granulated, 500 g 30224.50 1
Temperature probe Pt 100 11759.01 1 Copper(II) sulphate, anhydride, 250 g 31495.25 1
Calorimeter, transparent 04402.00 1 Copper(II) sulphate, 250 g 30126.25 1
Heating coil with sockets 04450.00 1 Water, distilled, 5 l 31246.81 1
Work and power meter 13715.93 1 PC, Windows® 95 or higher

Fig. 1. Experimental set-up.

PHYWE series of publications • Laboratory Experiments • Chemistry • © PHYWE SYSTEME GMBH & Co. KG • D-37070 Göttingen P3020711 1
 LEC
Determination of the hydration enthalpy of an electrolyte
02.07

Set-up and procedure heating and read the exact quantity of electrical energy supplied.
Set up the experiment as shown in Fig. 1 but for the time being After a further three minutes, stop recording the temperature.
do not connect the heating coil to the work and power meter. Figs. 3 and 4 show the graphs as they are presented by the pro-
Prepare the two copper salts by grinding each of them sepa- gramme when the measurements are stopped. If you use <sur-
rately to a fine powder in a mortar. Make sure that the anhydrous vey> from the toolbar you can read the temperature difference
copper sulphate really is anhydrous by heating it in a porcelain data.
dish over a Butane burner until it is completely white and allow- Repeat the experiment to determine the enthalpy of solution of
ing it to cool in a desiccator. Weigh 24.97 g (0.1 mol) of copper(II) the second copper salt. At least two measurements for each salt
sulphate and 15.96 g (0.1 mol) of anhydrous copper(II) sulphate should be performed to avoid errors and to calculate a mean
in two separate beakers (weighing accuracy 0.01 g). Fill the value.
calorimeter with 900 g of distilled water (weighing accuracy
0.1 g). Theory and evaluation
The dissolving of a solid electrolyte in water is primarily deter-
Connect the temperature probe to T1 of the measuring module. mined by two simultaneously occurring processes: the destruc-
Call up the ‘Measure’ programme in Windows and enter tion of the crystal lattice and the hydration of the ions.
<Temperature> as measuring instrument. Set the measuring The destruction of the crystal lattice is an endothermic process
parameters as shown in Fig. 2. Under <Diagram 1> select because energy is required to break down the chemical bonds,
Temperature T0a, the appropriate range for the temperature and whereas the hydration of the ions is exothermic. Depending on
the X bounds and ‘auto range‘. Now calibrate your sensor under the type of lattice, and on both the radius and the charge of the
<Calibrate> by entering a temperature value measured with a ions (charge density), the resulting enthalpy of solution can be
thermometer and pressing <Calibrate>. After having made these either endothermic or exothermic.
settings, press <Continue> to reach the field for the recording of
measured values. Arrange the displays as you want them.
Place the filled calorimeter on the magnetic stirrer, insert the oval
magnetic stirrer bar and switch on the stirrer (Caution: Do not
switch on the heating unit by mistake!). Insert the heating coil Fig. 3: Temperature-time curve of solution of copper(II) sulphate
and the temperature probe into the lid of the calorimeter and fix and determining the heat capacity of the system
them in position.

When temperature equilibrium has been reached (after approxi-

mately 10 min) start the measurement by pushing <Start mea-
surement>. Wait 3 to 4 minutes, then add the first copper salt to
the water by pouring it through the powder funnel which has
been inserted in the opening of the lid. Make sure that the entire
quantity of salt is added to the water without any loss. Continue
to measure until a new equilibrium has been reached. Sub-
sequently perform electrical calibration to determine the total
heat capacity of the calorimeter. Supply 10 V AC to the work and
power meter for the electric heating. Push the <Reset> button
and then put the free ends of the heating coil connection cables
into the output jacks. The system is now continuously heated
and the quantity of energy supplied is measured. When the work
and power meter shows approximately 4000 Ws, switch off the

Fig. 2: Measurement parameters

Fig. 3: Temperature-time curve of solution of anhydrous cop-
per (II) sulphate and determining the heat capacity of the
system

2 P3020711 PHYWE series of publications • Laboratory Experiments • Chemistry • © PHYWE SYSTEME GMBH & Co. KG • D-37070 Göttingen
 LEC
Determination of the hydration enthalpy of an electrolyte
02.07

When a salt exists in both hydrated and dehydrated forms, and The integral enthalpy of solution can be calculated according to
on assuming that when the hydrated salt dissolves only the equation (3).
degradation of the crystal lattice occurs, the enthalpy of hydra-
tion can be calculated using Hess’s theorem. Qexp
∆LH
(2)
n

Diagram of Hess’s theorem ∆Texp

Qexp
Qcal · (3)
∆Tcal
∆HHCuSO
[CuSO4]s 4 [CuSO4•5 H2O]s

Qexp Heat of solution of a salt

Qcal Electrical work for calibration
+ H2O + H2O ∆Texp Temperature difference during the dissolution of the
∆LHCuSO ∆LHCuSO
4•5 H2O salt
4
∆Tcal Temperature difference during the calibration
n Quantity of salt (CuSO4)
Cu2
aq SO2
4 aq

Data and results

MCuSO = 159.6 g · mol-1
4
MCuSO •5H O = 249.68 g · mol-1
4 2
∆Lh ∆LHCuSO = - 66.2 kJ · mol-1
∆LH
(1) 4
∆LHCuSO •5H O = + 11.5 kJ · mol-1
n 4 2
∆HHCuSO = - 77.7 kJ · mol-1
4
∆HHCuSO =∆LHCuSO -∆LHCuSO
4 4 4•5H2O

∆HH Enthalpy of hydration

∆LH Molar enthalpy of solution
∆Lh Integral enthalpy of solution

PHYWE series of publications • Laboratory Experiments • Chemistry • © PHYWE SYSTEME GMBH & Co. KG • D-37070 Göttingen P3020711 3
 LEC
Determination of the hydration enthalpy of an electrolyte
02.07

4 P3020711 PHYWE series of publications • Laboratory Experiments • Chemistry • © PHYWE SYSTEME GMBH & Co. KG • D-37070 Göttingen