Practical 5

Aim

: To investigate the effect of concentration on the electromotive force of a cell.

Materials

: EC1is 1.0 mol dm-3 aqueous copper (ll) nitrate EC2 is 2.0 mol dm-3 aqueous zinc nitrate EC3 is 1.0 mol dm-3 aqueous zinc nitrate EC4 is 0.1 mol dm-3 aqueous zinc nitrate EC5 is 0.01 mol dm-3 aqueous zinc nitrate EC6 is 0.001 mol dm-3 aqueous zinc nitrate A saturated solution of potassium chloride

Apparatus

: 2V accumulator, potentiometer, jockey, zinc plate, copper plate, measuring cylinder, beaker, filter paper, galvanometer, connecting wires with crocodile clips.

Diagram

Procedure

: 1. By means of measuring cylinder, beaker A with 50.0 cm 3 of EC1 and beaker B with 50 cm3 of EC2 was filled. 2. A strip of filter paper was immersed into the saturated solution of potassium chloride; then the end of the filter paper was dipped into the two beakers A and B to build the salt bridge. 3. The copper and zinc plates was cleaned with sandpaper, washed with distilled water, and dried. 4. The copper plate was clipped with the crocodile clip and it was connected to the end of the potentiometer to which the positive terminal of the accumulator is connected. 5. The zinc metal was connected to a galvanometer to which a jockey was attached. 6. The negative terminal of the accumulator was then connected to the other end of the potentiometer as shown in figure 5. 7. The two metal plates were dipped into their respective solutions. After one minute has elapsed, the jockey was touched along the length of the potentiometer wire until the galvanometer was showed a zero reading indicating no current flow. The jockey was did not slide along the length of the potentiometer wire to avoid a buildup of resistance.

8. The length of the potentiometer wire was note downed as x cm and the reading was recorded in the table below. 9. The experiment above was repeated by replacing solution EC2 with solutions as showed in the table below. New filter paper had been used for every new solution. 10. Ecell was calculateds using the following formula.

E0cell -

x length of potentiometer wire

2V

Safety precautions: 1. Do not slide the jockey along the length of the potentiometer wire to avoid a buildup of resistance.
2. New filter paper is used for every new solution

3. Wear lap coat before doing experiment

Result:

Length of potentiometer wire = 97.0 cm

Experimen t 1 2 3 4 5

Beaker A 50 cm3 EC1 50 cm3 EC1 50 cm3 EC1 50 cm3 EC1 50 cm3 EC1

Beaker B 50 cm3 EC2 50 cm3 EC3 50 cm3 EC4 50 cm3 EC5 50 cm3 EC6

Length of wire, x/cm 46.5 47.5 48.5 49.5 56.0

Ecell/V 0.964 0.984 1.005 1.026 1.161

[Zn+2]/moldm-3 0.1 0.05 0.005 0.0005 0.00005

Interpreting data:

Experiment 1: In 1 litre or 1000cm3 of solution, there is 2moles of Zn(NO3)2 in 1 dm-3. In 50cm3 of solution, there is 2moles/dm-3 x 50cm3 1000cm3 [Zn+2] = 0.1mol dm-3

Experiment 2: In 1 litre or 1000cm3 of solution, there is 2moles of Zn(NO3)2 in 1 dm-3. In 50cm3 of solution, there is 1.0moles/dm-3 x 50cm3 1000cm3 [Zn+2] = 0.05mol dm-3

Experiment 3: In 1 litre or 1000cm3 of solution, there is 2moles of Zn(NO3)2 in 1 dm-3. In 50cm3 of solution, there is 0.1 moles/dm-3 x 50cm3 1000cm3 [Zn+2] = 0.005mol dm-3 Experiment 4: In 1 litre or 1000cm3 of solution, there is 2moles of Zn(NO3)2 in 1 dm-3. In 50cm3 of solution, there is 0.01 moles/dm-3 x 50cm3 1000cm3 [Zn+2] = 0.0005mol dm-3

Experiment 5: In 1 litre or 1000cm3 of solution, there is 2moles of Zn(NO3)2 in 1 dm-3. In 50cm3 of solution, there is 0.001 moles/dm-3 x 50cm3 1000cm3 [Zn+2] = 0.00005mol dm-3

Calculation of E cell/V :

0 cell

X X length of potentiometer wire

2V

Experiment 1: E0cell = 46.5cm /96.5cm x 2V = 0.964V

Experiment 2: E0cell = 47.5cm/96.5cm x 2V = 0.984V

Experiment 3: E0cell = 48.5cm/96.5cm x 2V = 1.005V

Experiment 4: E0cell = 49.5cm/96.5cm x 2V = 1.026V Experiment 5: E0cell = 56.0cm/96.5cm x 2V = 1.161V

Discussions: From the result, we find out that when we decrease the concentration of the Zn2+ ion, the electromotive force of the cell is increases. Thus, it shows that when the concentration of the electrolyte solution in the negative terminal decreases, the electromotive force (emf) is increase as well. The half ionic equation that takes place in this experiment at the negative terminal is Zn(s) Zn2+ + 2e

We can use Nernst equation to determine the concentration of a reactant or product by measuring the emf of the cell. E = E - (0.059/N) log Q

The standard emf is calculated by adding together the Eo values for each half reaction:

Eocell = Eoreduction - Eooxidation

So, standard potential for copper and zinc electrolysis = 0.34 (-0.76) =1.10V According to Le Chateliers principle, when the concentration of Zn2+ is decreased, the reaction will displace towards the right. This will make the value of E 1.10V. Finally, in standard potential reaction: Zn(s) + Cu2+ (aq) Zn2+ (aq) + Cu(s)..........................E cell =1.10V
cell

more than

In this case n= 2(two electrons are transferred from Zn to Cu +2) and the standard emf is+1.10V. E = E - (0.0592V/n) log Q

E = 1.10V- (0.0592V/2) log [Zn+2]/[Cu2+] The emf increases as [Cu+2] increases and as [Zn+2] decrease. From the result obtained, [Cu+2] is 1.0 moldm-3 and [Zn+2] is 0.001mol dm-3. E= 1.10V- (0.0592V/2) log [0.001mol dm-3.]/[ 1.0 moldm-3] E= 1.10V- (0.0592V/2) (-3.00) = 1.19V Thus, increasing the concentration of the reactant (Cu +2) and decreasing the concentration of the product (Zn+2) relative to standard conditions increases the emf of the cell(Ecell = +1.19 V) relative to standard conditions (E0= +1.10V). The result was obtained was similar to Le Chateliers principle.

So, the experiment shows that if the concentration of reactants increase relative to those of products, the emf increase. Conversely, if the concentration of the products increase relative to reactants, the emf deacrease.

However, when the concentration of Zn2+ is increased, the reaction will displace towards the left and the value of E
cell

will be less than 1.10V. Otherwise, when the

concentration of Zn2+ is decreased, the reaction will displace towards the right and the value of E cell more than 1.10V.

Conclusion: When the Concentration of aqueous zinc Nitrate increase, the electromotive (emf) force of the cell will be decrease. And when the concentration of aqueous zinc Nitrate decrease, the electromotive (emf) force of the cell will be increase.

Questions: 1. Write a cell diagram for the electrochemical system Zn(s) I Zn2+ (aq) Cu2+ (aq) I Cu(s)

2. Write half-life equations taking place in beakers A and B and hence write an equation for the overall cell reaction. Beaker A: Cu2++ 2e- Cu Beaker B: Zn Zn2+ + 2eOverall : Cu2++ Zn Cu+Zn2+

3. Plot a graph of E cell against lg [Zn+2] in beaker B and explain how the emf of the cell varies with the concentration of Zn+2 in beaker B. Log [Zn+2]/moldm-3 Log 0.1= -1 Log 0.05 = -1.30 Log 0.005 = -2.30 Log 0.0005 = -3.30 Log 0.00005 = -4.30

When the concentration of Zn2+ is decrease, the emf of the cell will increase. While the concentration of Zn2+ is increase mean, the emf of the cell will decrease.

4. Explain what will happen to the E cell value if I. The solution in beaker A is replaced with 0.1 mol dm -3 aqueous copper(ll) nitrate,

According to Le Chateliers principle, when the concentration of

Cu 2+(aq)

decreases, the tendency of Cu2+(aq) to form Cu decreases. This will make the half-cell become a less powerful oxidising agent. As a result, the electrode potential becomes less positive. The half cell equation of Copper ion is as follows; Cu2+(aq) + 2eCu(s) And the equilibrium will shift towards left hand side and hence more Cu 2+ ions will be produced and it will cause the copper plate to be more negatively charged. So that, more electrons will be produced and it will leads the electrode potential to become more negative and thus decreases the E cell value as well.

II.

The solution in beaker B is replaced with 0.1 mol dm-3 aqueous aluminum chloride, and the plate of zinc metal is replaced with aluminum metal?

If the solution in beaker B is replaced with 0.1 moldm -3 aqueous aluminium chloride, and the plate of zinc metal is replaced with aluminium metal, the Ecell value for the reaction between copper (II) nitrate and aluminium nitrate will lower than the Ecell value of the reaction between copper (II) nitrate and zinc nitrate. It is because, for 1 mol of nitrate solution, zinc produces 2 moles of electrons but for aluminium, it will produce 3 moles of electrons. Thus, aluminium will cause the aluminium electrode value to become more negatively-charged due to the higher production of electrons compared to zinc of the same amount. Hence, the E cell value will become lower when aluminium is used.

BIBLIOGRAPHY

INTERNET RESOURCES Retrived from, http://www.ausetute.com.au/calcelemf.html http://www.tutorvista.com/content/chemistry/chemistryiv/electrochemistry/nernst-equation-cell.php http://www.springerlink.com/content/v8p70g0680h55703/ On 2 Mac 2009.

BOOK Toon, T. Y. (2003). Physical Chemistry For STPM. Shah Alam: Penerbit Fajar Bakti Sdn. Bhd. Lim You Sie., Yip Kim Hong.(2007). Pre-U STPM Physical Chemistry. Rawang: Pearson Longman.

Brown.L.T., Jr.Lemay.E.H.(2003). Chemistry For The Central Science.United states Of America.Pearson education International.