CONCENTRATION CELL Concentration cells are galvanic cells made up of two similar electrodes dipped into solutions of the same substance having different concentrations. Or They are galvanic cells with metallic electrodes which are an alloy of two metals dipped in a salt solution of one of the metals, the concentration of this metal being different in the electrodes. Concentration cells are those whose EMF depends on the concentration difference. Types of concentration cells They are broadly calssifed as (i) Electrode concentration cells These cells are made up of two electrodes having different concentration of metals which are immersed in same solution of their salt. Thus in such cells electrolyte strength is same (ii)Electrolyte concentration cells These cells are made up of two electrodes which are of the same material and are immersed into two solution of the same electrolyte having different concentrations. Dr. R. Anand/B.Tech/Electrochemistry Page 1 of 12ELECTRODE CONCENTRATION CELLS Gas concentration cells: (hydrogen gas electrode) The electrodes are made up of same gas having different activities and immersed in solution containing gas ions. The gases most commonly used for the preparation of gas electrodes are H., Cl,, O, etc. These are immersed into H+, Cl and O ions respectively. The cell potential of such cells is found to depend upon the pressure of gases and also the concentration of gas ions. e.g. Hydrogen gas electrode — in such a cell when both the electrodes are hydrogen electrodes but the partial pressure of hydrogen are different at two electrodes which are dipped in solution containing H* ions whose activity is “1. If P, and P, are the partial pressures of hydrogen at two electrodes then the cell can be represented as Hz (Py, = P1) | H+ | Ho(Py, = P2) The electrode reactions at the two electrodes can be represented as Oxidation: 1/2 H, (P;) W+e Applying Nernst equation for the reduction part of the above reaction RT /|P,)3/2 Evepe = Eh, — = Dr. R. Anand/B.Tech/Electrochemistry Page 2 of 12But £j;, =9 Therefore Rie aera ; Evefe = —— In at H RT LP, ]1/2 Reduction: H’ +e 1/2, H2 (Pr) Bright = Sai ayy The overall cell reaction of this cell can be represented as 1/2 H, (P;) ———>_ 1/2 H, (P,) And the cell EMF is given by E¢eu =)Erignt — Eieft 1 1 Rie [P2|2 RT |Py 2 Cell = ae n ay+ Fo aye RT a RT z Ecen = - = (InP, “= nay) +=(InlP, 2 = Ina) = el ae BG ee Re a ine See Tyger igs aes igi RT Py The cell EMF depends upon the partial pressure of Eceii ==> In— _ hydrogen at the two electrodes. However, the ae, concentration of H* has no effect on cell EMF. Dr. R. Anand/B.Tech/Electrochemistry Page 3 of 12ELECTROLYTE CONCENTRATION CELLS They are further classified as (i) Concentration cells without transference (or transport) (ii) Concentration cell with transference (transport) ELECTROLYTE CONCENTRATION CELLS WITHOUT TRANSFERENCE (a) In which the two electrodes are same, but electrolytes are of different concentrations and are connected by a bridge. Consider a cell having both its electrodes made up of hydrogen electrodes. It can be represented as H, (1 atm) | H* (a,) | H* (a,) | H,,(1 atm) The reaction on the left electrode where oxidation occurs is %H,(1atm) > H* (a,)+ & To apply Nernst equation, the above equation is written as H* (a,) + e/—> % H,(1 atm) Electrode potential of left hand electrode is Rta 0 Eiett = Eqe jy, — In e HY/H2 MELE dat Or. R. Anand/B.Tech/Electrochemistry Page 4 of 120 = RT But Ej), =0 Therefore Bett = i ay The reaction occurring on the right hand electrode (reduction) can be represented as V atm H* (a,) +e > %H,(1 atm) se Hy At V atm And the electrode potential is RT Eight = 7 ag HY (Activit H’ (Activity = a2) The overall cell reaction is H* (a,) + H* (a,) RT RT And the Cell EMFis Even = Erighe ~ Eiere = > ay — = in ay RT ag Sn F ay Above equation shows that for 1 Faraday of electricity to be produced, 1 mole of H* ions are transferred from solution of activity a, to the solution of activity a,. This transfer of H* ions occurs indirectly (through the salt bridge). Moreover, from this equation it is clear that to get a positive value of E...,,, a, >a, Or. R. Anand/B.Tech/Electrochemistry Page 5 of 12ELECTROLYTE CONCENTRATION CELLS WITHOUT TRANSFERENCE (b) Electrolytic concentration cell without transference obtained by combination of two chemical cells Such a cell can be illustrated if we consider the following cell H, (1 atm), | HCI (a,), AgCl(s) | Ag This cell consists of hydrogen electrode and the silver-silver chloride electrode which are dipped in the same solution of HCI of activity a,. The net cell reaction is %H, (1 atm) + AgCl = Ag + HCI (a,) Using Nernst equation, the cell EMF of this cell is a RT Eceu = Eag,agct — an ay (Remember n = 1 and activities of Ag, AgCl and H, at 1 atm is taken as unity) Again consider the same cell but with a different activity of HCI (a,), then we have H, (1.atm) | HCI (a,), AgCl(s) | Ag The net cell reaction is YH, (1 atm) + AgCl = Ag + HCI (a) Or. R. Anand/B.Tech/Electrochemistry Page 6 of 12Using Nernst equation, the cell EMF of this cell is ‘i RT Ecen = Eagagci — a2 If the above two cells are connected in such a way that they oppose each other the cell so formed can be represented as H, (1 atm) | HCI (a,), AgCl(s) | Ag — Ag | AgCl(s), HCI (a,), | H, (1 atm) The overall cell reaction will be %AH, (1 atm) + AgCl — % H, (1 atm) — AgCl = Ag + HCI (a,) — Ag — HCI (a,) HCl (a,) = HCI (a,) The EMF of this cell will be F RT r RT Eceu = (Exeage —ain ai) > (E%gagct —>in az) RT ag Eceu = reins From the above equation, we can say that if 1 Faraday of electricity passes through the cell, it brings about an overall transfer of 1 mole of HCI from the solution of activity a, to a solution of activity a,. So it constitutes an electrolytic concentration cell. Since there is no direct transfer of electrolyte (viz. HCI) from one solution to the other, it is an electrolytic concentration cell without transference. Dr. R. Anand/B.Tech/Electrochemistry Page 7 of 12ELECTROLYTE CONCENTRATION CELL WITH TRANSFERENCE These cells consist of two identical electrodes immersed in two solution of the same electrolyte at different concentrations. The electrodes should be reversible to one of the ions of the electrolyte. The tow electrolytes are somehow prevented from mechanical mixing by means of a porous diaphragm as in the case of a Daniell cell. A simple concentration cell with liquid junction potential is Pt | H, (1 atm) | HCI (a,) | HCI (a,) | H, (1.atm) | Pt If a, >a, the following reaction occurs at the electrode immersed in the solution with activity a, % H,(1 atm) > Ht (a,)+ e— Reduction takes place at right hand electrode H*(a,) + e~ > %H,(1 atm) The overall reaction is BEML) F > HP (2h) sasertnasnrsasnsrsnsnnntnasecnnaceee (i) Process taking place at the liquid junction: Electrons flow in the external circuit from left to right. However as H* ions are produced in the left electrode and Cl~ ions are left in the right electrode, the inner circuit is completed by the transference of Cl— ions from right to left and the transference of H* ions form left to right across the liquid junction. Dr. R. Anand/B.Tech/Electrochemistry Page 8 of 12If the transport number of CI- ions is represented by t_, then for one Faraday of electricity passing through the cell, t_ gram equivalents of the CIT | 'h — ions will be transferred from right to left (i.e. from solution of activity a, to the solution of activity a,) HCI (ay) HCI (a3) #.Cl= (alt Hel (aetna ccacesaseall) Liquid Junction Further, transport number of H* ions = 1— t_ Therefore during the same time, (1— t_) gram equivalent of H' ions will be transferred from left to right i.e. from solution of activity a, to solution of activity a, (1 t_) Ht (AQF Phe AB 5 bipp Wonnensrseseseccvsetarcecernnisnsaerscnans (iii) Overall process: To calculate the net transfer of the material, equations (i), (ii) and (iii) must be added H* (a,) + t_ CI (a,) + (1— t_) H*(a,) = H* (a,) +t_ I~ (a,) + (1— t_) H*(a,) or t_H*(a,)+t_Cl- (a,) = t2H* (a;)+t_ Cl> (a,) or PORC (as) = 8 HE a) ranrciverninr nie (iv) Or. R. Anand/B.Tech/Electrochemistry Page 9 of 12This equation tells that for one faraday of electricity passing through the cell, t_ gram equivalents of HCl from the solution of activity a, are transferred to the HCI solution of activity a,. Therefore for the passage of one Faraday of electricity through the cell, one full gram equivalent of HCI is transferred. Applying Nernst equation to the process (iv) the EMF of the cell is given by For EMF to be positive, a, > a, Or. R. Anand/B.Tech/Electrochemistry Page 10 of 12LIQUID JUNCTION POTENTIAL The potential set up at the junction of the two solutions because of the difference in the speeds of the ions moving across the boundary is called liquid junction potential. The EMF of a cell should thus not only be the sum of the oxidation potential (E,) of the electrode where oxidation occurs and reduction potential (E,) of the electrode where reduction occurs, but also should include the junction potential (E). E=E, +E, +E; However, the type of junction employed most commonly is the salt bridge containing an electrolyte such as KCI. It is believed that the K+ ions and Cl- ions move almost with equal speed and thus the junction potential is almost reduced to zero. In such a case, the EMF of the cell can be simply taken as E=F +E, Dr. R. Anand/B.Tech/Electrochemistry Page 11 of 12TRANSPORT NUMBER The fraction of the total current carried by an ion is called its transport number or transference number or Hittorf’s number Greater the speed of the ion, greater the amount of current it will carry with it and hence greater will be its transport number Transport number for an ion is not constant. It depends upon the second ion which is present in the salt. Or. R. Anand/B.Tech/Electrochemistry Page 12 of 12