Scribd Logo
Upload

Welcome to Scribd!

  • 450 views

    Capitulo 24 Skoog

    Uploaded by

    Erick de la Rosa
    This chapter discusses principles of instrumental analysis including electrochemical cells and controlled potential electrolysis. Example calculations are provided for determining cell potentials and quantities of substances from electrolysis experiments. Cell potentials are calculated using the Nernst equation. Controlled potential electrolysis can be used to selectively deposit analytes from solution or separate mixtures based on differences in standard potentials. Calculations include determining quantities of deposited substances, electrolysis times required, and cell potentials needed for selective deposition or separation.

    Copyright:

    Attribution Non-Commercial (BY-NC)
    Download as PDF, TXT or read online from Scribd

    Capitulo 24 Skoog

    Uploaded by

    Erick de la Rosa
    450 views7 pages
    This chapter discusses principles of instrumental analysis including electrochemical cells and controlled potential electrolysis. Example calculations are provided for determining cell potentials and quantities of substances from electrolysis experiments. Cell potentials are calculated using the Nernst equation. Controlled potential electrolysis can be used to selectively deposit analytes from solution or separate mixtures based on differences in standard potentials. Calculations include determining quantities of deposited substances, electrolysis times required, and cell potentials needed for selective deposition or separation.

    Original Title

    capitulo 24 skoog

    Copyright

    © Attribution Non-Commercial (BY-NC)

    Available Formats

    PDF, TXT or read online from Scribd

    Did you find this document useful?

    Is this content inappropriate?

    This chapter discusses principles of instrumental analysis including electrochemical cells and controlled potential electrolysis. Example calculations are provided for determining cell potentials and quantities of substances from electrolysis experiments. Cell potentials are calculated using the Nernst equation. Controlled potential electrolysis can be used to selectively deposit analytes from solution or separate mixtures based on differences in standard potentials. Calculations include determining quantities of deposited substances, electrolysis times required, and cell potentials needed for selective deposition or separation.

    Copyright:

    Attribution Non-Commercial (BY-NC)
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    450 views7 pages

    Capitulo 24 Skoog

    Uploaded by

    Erick de la Rosa
    This chapter discusses principles of instrumental analysis including electrochemical cells and controlled potential electrolysis. Example calculations are provided for determining cell potentials and quantities of substances from electrolysis experiments. Cell potentials are calculated using the Nernst equation. Controlled potential electrolysis can be used to selectively deposit analytes from solution or separate mixtures based on differences in standard potentials. Calculations include determining quantities of deposited substances, electrolysis times required, and cell potentials needed for selective deposition or separation.

    Copyright:

    Attribution Non-Commercial (BY-NC)
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    of 7

    Skoog/Holler/Crouch

    Principles of Instrumental Analysis, 6th ed.

    Chapter 24
    Instructors Manual

    CHAPTER 24
    24-1. (a)

    2Pb2+ +2H2O U Pb(s) + O2 +4H+


    Pb2+ + 2e U Pb(s)

    E0 = 0.126V

    O2(g) + 4H+ + 4e U 2H2O

    E0 = 1.229 V

    Eright = 0.126
    Eleft = 1.299

    0.0592
    1
    = 0.1556 V
    log
    2
    0.100

    0.0592
    1
    = 1.1862 V
    log
    4
    0.800 (0.200) 4

    Ecell = 0.1566 1.1862 = 1.342 V


    (b)
    24-2. (a)

    0.250 0.950 = 0.238 V


    To lower M1 to 2.00 104.
    E1 = EM0 1

    0.0592
    1
    log
    = EM0 1 0.109 V
    2
    2 104

    M2 begins to deposit when


    E2 = EM0 2 0.0592 log

    1
    = EM0 2 0.0592
    0.100

    When E2 = E1, the concentration of M1 will be reduced to 2.00 104 and M2will not
    have begun to deposit. That is,
    EM0 2 0.0592 = EM0 1 0.109 V

    EM0 2 EM0 1 = E 0 = 0.109 ( 0.0592) = 0.050 V

    Principles of Instrumental Analysis, 6th ed.

    Chapter 24

    Charge on M2

    Charge on M1

    1
    2
    3
    2
    2

    2
    2
    1
    1
    3

    (a)
    (b)
    (c)
    (d)
    (e)
    24-3. Ag+ + e U Ag(s)

    E0 = EM0 2 EM0 1 , V
    0.109 + 0.0592 = 0.050
    0.109 + 0.0296 = 0.079
    0.219 + 0.020 = 0.199
    0.219 + 0.0296 = 0.189
    0.073 + 0.0296 = 0.043

    E0 = 0.799 V

    Cu2+ + 2e U Cu(s)

    E0 = 0.337 V

    BiO+ + 2H+ + 3e U Bi(s) + H2O

    E0 = = 0.320 V

    (a) First, we calculate the potentials vs. Ag-AgCl needed to reduce the concentrations to
    106 M. For Ag+,
    Ecell = 0.799 0.0592 log

    1
    0.199 = 0.444 0.199 = 0.245 V
    1.00 106

    For Cu2+
    Ecell = 0.337

    0.0592
    1
    log
    0.199 = 0.040 V
    2
    1.0 106

    For BiO+
    Ecell = 0.320

    0.0592
    1
    log
    0.199 = 0.009 V
    6
    3
    1.0 10 (0.5) 2

    Bi(s) begins to deposit when


    Ecell = 0.320

    0.0592
    1
    log
    0.199 = 0.084 V
    3
    0.0550 (0.5) 2

    Cu(s) begins to deposit when


    Ecell = 0.337

    0.0592
    1
    log
    0.199 = 0.111 V
    2
    0.125
    2

    Principles of Instrumental Analysis, 6th ed.

    Chapter 24

    (b) Silver could be separated from BiO+ and Cu2+ by keeping the cell potential greater
    than 0.111 V. Cu2+ and BiO+ cannot be separated by controlled-potential electrolysis.
    24-4. We calculate the potentials at which the silver salts first form
    For I, Ecell = 0.244 (0.151 0.0592 log 0.0250) = 0.300 V
    For Br, Ecell = 0.244 (0.073 0.0592 log 0.0250) = 0.076 V
    For Cl, Ecell = 0.244 (0.222 0.0592 log 0.0250) = 0.073 V
    (a)

    AgI forms first at a potential of 0.0300 V (galvanic cell).

    (b)

    When [I] 105 M


    Ecell = 0.244 (0.151 0.0592 log 105) = 0.099 V

    AgBr does not form until Ecell = 0.076 V so the separation is feasible if the Ecell does is
    kept above 0.076 V.
    (c)

    I could be separated from Cl by maintaining the cell potential above 0.073 V.

    (d)

    For [Br] 105 M


    Ecell = 0.244 (0.073 0.0592 log 105) = 0.125 V

    But AgCl forms at a cell potential of 0.073 V, so separation is not feasible.


    24-5. (a)

    (b)

    Ecell = 0.854

    0.0592
    1
    log 6 0.244 = 0.432 V
    2
    10

    Kf = 1.8 107 =

    [Hg(SCN) 2 ]
    [Hg(SCN) 2 ]
    =
    2
    2+
    [Hg ][SCN ]
    [Hg 2+ ](0.150) 2

    [Hg(SCN)2] + [Hg2+] = 106


    Because of the large amount of SCN, we can safely assume that [Hg2+] << [Hg(SCN)2]
    Substituting into the expression for Kf, we find

    Principles of Instrumental Analysis, 6th ed.


    1.8 107 =

    Chapter 24

    1.00 106
    [Hg 2+ ] (0.150) 2

    [Hg2+] = 2.47 10-12


    0.0592
    1
    log
    0.244 = 0.266 V
    2
    2.47 1012

    Ecell = 0.854
    (c)

    With a large [Br], we can assume [Hg2+] + [HgBr42-] [HgBr42-] = 1.00 106
    0.0592
    (0.150) 4
    log
    0.244 = 0.101 V
    2
    1.00 106

    Ecell = 0.223
    24-6. (a)

    Co2+ + 2e U Co(s)
    To deposit 0.270 g of Co(s) would require the following charge
    Q = 0.270 g

    1 mol Co
    2 mol e
    1F
    96485 C

    = 8.841 102 C

    58.93 g
    mol Co
    mol e
    F

    Q = It so t = Q/I
    t = 8.841 102 C/0.750 C/s = 1178.8 s or 19.6 min
    (b)

    3 Co2+ + 4 H2O U Co3O4(s) + 8H+ + 2e

    Q = 0.270 g

    3 mol Co2+ consumed per 2 mol e

    1 mol Co
    2 mol e
    1F
    96485 C

    = 2.947 102 C

    58.93 g
    3 mol Co
    mol e
    F

    t = 2.947 102 C/0.750 C/s = 392.95 s or 6.55 min


    24-7. (a)

    Q = 0.300 g

    1 mol Tl
    3 mol e
    1F
    96485 C

    = 4.249 102 C

    204.37 g
    mol Tl
    mol e
    F

    t = Q/I = 4.249 102 C/0.905 C/s = 469.5 s or 7.83 min


    (b)

    2Tl+ + 3 H2O U Tl2O3(s) + 6H+ + 4 e-

    2 mol Tl+ consumed per 4 mol e

    Principles of Instrumental Analysis, 6th ed.


    Q = 0.300 g

    Chapter 24

    1 mol Tl
    4 mol e
    1F
    96485 C

    =283.27 C

    204.37 g
    2 mol Tl
    mol e
    F

    t = 283.27 C/0.905 C/s = 313.00 s or 5.22 min


    (c)

    Proceeding as in part (a), with the only difference being 1 mol e/mol Tl
    Q = 141.63 C
    t = 156.5 s or 2.61 min

    24-8. Sample 1 at 1.0V

    at 1.80 V

    11.63 C

    68.60 C

    2 mol CCl4
    1 mol e

    = 1.25 104mol CCl4


    96485 C
    2 mol e

    2 mol CHCl3
    1 mol e

    = 2.370 104 mol CHCl3

    96485 C
    6 mol e

    original no. mol CHCl3 = 2.370 104 1.205 104 = 1.165 104
    1.205 104 mol CCl4 153.82 g CCl4 / mol CCl4
    100% = 2.47% CCl4
    0.750 g sample
    1.165 104 mol CHCl3 119.37 g CHCl3 / mol CHCl3
    100% = 1.85% CHCl3
    0.750 g sample

    In a similar manner, we can calculate the other percentages as shown in the spreadsheet.

    Principles of Instrumental Analysis, 6th ed.

    Chapter 24

    24-9. 1 mol As2O3 = 2 mol HAsO32- = 2 mol I2 = 4 mol e


    Q = 0.1276 C/s (11 min 60 s/min + 54 s) = 91.106 C
    Mass As2O3 =

    %As2O3 =

    1 mol As 2 O3
    197.8 g As 2 O3
    91.106 C

    = 0.04669

    96485 C/mol e
    4 mol e
    mol

    0.04669 g
    100 = 0.731
    6.39

    24-10. The equivalent mass of an acid is that mass that contains one mole of titratable H+.
    0.0441 C/s 266 s

    equiv mass =

    1F
    1 equiv HA

    = 1.216 104 equiv HA


    96485 C
    F

    0.0809 g HA
    = 665 g/equiv
    1.216 104 equiv HA

    24-11. 1 mol C6H5NH2 = 3 mol Br2 = 6 mol e


    Q = (3.76 0.27) min 60 s/min 1.00 103 C/s = 0.2094 C
    mol C6H5NH2 = 0.2094 C

    1 mol C6 H 5 NH 2
    1 mol e

    = 3.617 107
    96485 C
    6 mol e

    mass C6H5NH2 = 3.617 107 mol C6 H 5 NH 2


    = 33.7 g
    24-12. The spreadsheet is attached.

    93.128 g
    106 g/g
    mol C6 H 5 NH 2

    Principles of Instrumental Analysis, 6th ed.

    Chapter 24

    You might also like