Chapter 7 Electrochemistry 7.2 Conductivity and its application
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1 Chapter 7 Electrocheistry 7.2 Conductivity and its application Out-class extensive reading: Levine: pp , 16.5 electric conductivity 16.6 Electrical conductivity of electrolyte solutions
2 Key proble: How to evaluate the ability of an electrolytic solution to conduct electricity?
3 1. Soe concepts For etals: Oh s Law R R I l A 7.2 Conductivity and its application R: resistance, nit: Oh, : resistivity nit: D For electrolyte solution: electric conductance (G) : Definition: G = 1/R nit: -1, ho, Sieens, S Reciprocal of resistance conductivity () : Definition: = 1/ nit: S -1 A R 1 R 2 G R 4 C R 3 B G A l I ~ Wheatstone Bridge Circuit
4 2. Measureent of conductance: Conductance cell and conductance electrode conductance cell conductance electrode with sooth or platinized platinu foil electrodes
5 2. Measureent of conductance: F D a capacitor! A R 2 R 1 R 2 G R 4 C R 3 B High-frequency alternative current, ca Hertz? I ~ R 3 R 2 = R 4 R 1 R 1 R 2 R R 4 3 G 1 R 1 G A l Conductoeter
6 2. Measureent of conductance: G l A K cell G Cell constant s R s x R x x Rs s Rx Calibration: The conductance cell is usually calibrated using standard aqueous KCl (potassiu chloride ) solution. c/ ol d / S EXAMPLE The conductance of a cell containing an aqueous ol d -3 KCl solution whose conductivity is is When the sae cell is filled with an aqueous ol d -3 NaCl solution, its conductance is Calculate the conductivity of the NaCl solution.
7 3. Influential factors of conductivity (1) Teperature 1.What can we learn for this experiental fact? ice 2. Why do we do electrolysis and electroplating using war electrolyte?
8 3. Influential factors of conductivity /S (2) Concentration LiCl KOH H 2 SO 4 What can we learn for this figure? Can you give explanation to these experiental facts? (1) c (2) axiu; (3) kinds MgSO 4 HAc c/ol d -3
9 4. Molar conductivity H 2 SO c c c Definition c/ol d -3 Why do we introduce the concept of olar conductivity?
10 4. Molar conductivity (2) Concentration-dependence of olar conductivity / S ol -1 2 KOH HCl KCl HAc NaOH NaCl (1) Why does olar conductivity decrease with increasing the concentration? (2) Does the curve shape inspire you? c / ol d -3
11 5. Kohlrausch s epirical forula / S ol HCl H 2 SO 4 Kohlrausch 0.02 KCl Why did Kohlrausch plot against c 1/2? Within what concentration range does the linear relation appear? 0.01 Na 2 SO 4 HAc c / ol d 3
12 5. Kohlrausch s epirical forula For strong electrolyte A c liiting olar conductivity Kohlrausch s Square Root Law In what concentration range is the Kohlrausch law applicable?
13 6. Kohlrausch s law of independent igration Electrolytes /S ol -1 c 2 HCl LiCl NaCl KCl The difference in of the two electrolytes containing the sae cation or anion is the sae. The sae differences in led Kohlrausch to postulate that olar conductivity at infinite dilution, / can be broken down into two contributions by the ions. LiNO NaNO KNO ,, ionic conductivities at infinite dilution
14 6. Kohlrausch s law of independent igration,, v v,, at infinite dilution is ade up of independent contributions fro the cationic and anionic species. Explanation to the sae difference (KCl) (NaCl),K,Cl,Na,Cl,K + +,Na (KNO ) (NaNO ) 3 3,K,NO,Na,NO,K,Na 3 3
15 How can we deterine the liiting olar conductivity of weak electrolyte (HAc) (H ) (Ac ) (H ) (Cl ) (Na ) (Ac ) (Na ) (Cl ) (HCl) (NaAc) (NaCl) (HAc) ( )S ol Key: 7.2 Conductivity and its application S ol -1-1,, -1-1 How to easure the ionic conductivity at infinite dilution?
16 7. Measuring liiting olar conductivity of ions C -, Z -, - ; C +, Z +, + ; B A C I + = A + Z + c + F I = A Z c F I = I + + I = Ac + Z + F( + + ) V F Z Ac G ( ) ) ( ) ( ) ( F Z c l V F Z c A l V F Z Ac A l G c F Z c ) ( 7.2 Conductivity and its application
17 For uni-univalent electrolyte: ) ( F,, F, F,, ( ) F F, t t, To easure,+ or,-, either t + and t - or + and - ust be deterined. c F Z c ) ( t t 7. Measuring liiting olar conductivity of ions 7.2 Conductivity and its application
18 Influential factors for 1) Nature of ions 7.2 Conductivity and its application ions r / n 10 2 ions r / n 10 2 H OH 1.98 Li F Na Cl K Br Mg CO Ca C 2 O Sr Fe(CN) Al Fe(CN) Fe La Charge; Radius; charge character; transfer echanis
19 Transport echanis of hydrogen and hydroxyl ions Grotthus echanis (1805) The ion can ove along an extended hydrogen-bond network. Science, 2002, 297:
20 Evolution of concepts Mind apping
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