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1.11 Rearrangement of equation 1.4.16 yields the following expression for / as a function of E, which is convenient for calculating i¡ªE curves for nernstian reactions: ilii = {1 + exp[(nF/RT)(E - El/2)]}-1 (a) Derive this expression, (b) Consider the half-reaction Ru(NH3)£+ + e *¡À Ru(NH3)^+. The E¡ã for this reaction is given in Appendix C. A steady-state i-E curve is obtained with a solution containing 10 mM Ru(NH3)6 + and 1 M KC1 (as supporting electrolyte). The working electrode is a Pt disk of area 0.10 cm2 operating under conditions where m = 10~3 cm/s for both Ru species. Use a spreadsheet program to calculate and plot the expected i-E curve. 1.12 (a) Derive an expression for / as a function of E, analogous to that in Problem 1.11, from equation 1.4.20, using (1.4.15) as the definition of §¦§è2, for use in solutions that contain both components of a redox couple, (b) Consider the same system as in Problem 1.11, but for a solution containing 10 mM Ru(NH3)^+ and 5.0 mM Ru(NH3)^+ in 1M KC1. Use a spreadsheet program to calculate the i-E curve and plot the results, (c) What is 77conc at a cathodic current density of 0.48 mA/cm2? (d) Estimate Rmt. [ Last edited by wolfghost on 2013-6-6 at 10:02 ] |
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wolfghost
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2Â¥2013-05-18 10:10:12
wolfghost: °ïÄã¸ÄÁËϱêÌ⣬ÈÃÓ¦ÖúµÄ³æ×ÓÄÜÖ±½ÓÃ÷°×ÄãÇóÖúµÄÄÚÈÝ£¡ 2013-06-06 10:03:09
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½â´ðÕâЩϰÌâ¡£1. 11 ÕûÀí¹«Ê½(1. 4. 16 ) ¿ÉµÃµ½ÏÂÃæ¼ÆËãÄÜË¹ÌØ·´Ó¦µÄi-E ÇúÏߵļò±ã±í´ïʽ: i/ il = {1 + exp [ ( nF/ R T) ( E - E1/ 2 ) ]} - 1 ( a ) ÍÆµ¼´Ë±í´ïʽ¡£( b) ¿¼Âǰ뷴Ӧ: Ru ( NH3 )3 + 6 + e Ru ( NH3 )2 + 6 , ÆäE􊯟 ¿ÉÓɸ½Â¼C ÖÐ²é µ½¡£ÔÚº¬ÓÐ10mmol/ L Ru (NH3 )3 + 6 ºÍ1mol/ L KCl ×÷Ϊ֧³Öµç½âÖʵÄÈÜÒºÖÐ, ¿ÉµÃµ½Ò»¸öÎÈ̬µÄi-E ÇúÏß¡£ÔÚÁ½ÖÖRu »¯ºÏÎïm = 10 - 3 cm/ s Ìõ¼þÏÂ, ²ÉÓÃÃæ»ýΪ0. 1cm2 µÄ²¬µç¼«½øÐÐʵÑé, ÀûÓóÌÐò½ø ÐмÆËã²¢»³öÔ¤ÆÚµÄi-E ÇúÏß¡£ 1. 12 ( a ) ÀàËÆÓÚϰÌâ1. 11 , ²ÉÓÃʽ( 1. 4. 15 ) ¶ÔÓÚE1/ 2 µÄ¶¨Òå, ´Ó¹«Ê½( 1. 4. 20) ÍÆµ¼³ö¿ÉÓÃÓÚÈÜÒºº¬ ÓÐÑõ»¯»¹ÔÁ½ÖÖ×é·ÖÇé¿öϵĵçÁ÷×÷ΪµçÊÆº¯ÊýµÄ±í´ïʽ; ( b) ¿¼ÂÇÓëϰÌâ1. 11 ÏàͬµÄÌåϵ, µ«ÈÜ ÒºÖк¬ÓÐ10mmol/ L Ru(N H3 )3 + 6 ¡¢5mmol/ L Ru( NH3 )2 + 6 ºÍ1mol/ L KCl, Ó¦ÓÃÒ»¸ö³ÌÐò½øÐмÆËã²¢ »³öÆäi-E ÇúÏß¡£( c ) ÔÚÒõ¼«µçÁ÷ÃܶÈΪ0. 48mA/ cm2 µÄÇé¿öÏÂ, ¦Çconc ÊǶàÉÙ? ( d) ¹ÀËãRmt ¡£ |

3Â¥2013-06-06 10:00:24














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