Your Federal Quarterly Tax Payments are due April 15th Get Help Now >>

General Chemistry - PowerPoint by fjhuangjun

VIEWS: 105 PAGES: 245

									(   (
• conjugate base.
• conjugate acid.

HA(aq) + H2O(l)     H3O+(aq)   +   A-(aq)
H2O(l) + H2O(l)        H3O+(aq) + OH-(aq)


        [H3O   ][OH- ]
K eq 
           [ H 2O ]2

K eq  [H 2O]  2  [H O  ][OH- ]
                     3

K w  [H3O  ][OH- ]  1.0  1014
                                 pOH pH

pH   log[H3O ]   log[H ]    pOH   log[OH- ]



 pH = pOH = 7.00                 :25 C           •
     [H+] > 1.0  10-7, pH < 7.00                 •
    [H+] < 1.0  10-7, pH > 7.0                   •
pOH pH
                    pOH pH
p X   log X
 pKw = -log Kw
Kw    [H  ][OH- ]  1.0  1014

              
pK w   log [H            
                    ][OH- ]  14

  log[ H  ]  log[OH- ]  14

pH  pOH  14
pH
• HCl, HBr, HI, HNO3, HClO3, HClO4, H2SO4

• HNO3(aq) + H2O(l)  H3O+(aq) + NO3-(aq)

• HNO3(aq)  H+(aq) + NO3-(aq)
• NaOH, KOH, Ca(OH)2).

• O2-(aq) + H2O(l)  2OH-(aq)

• H-(aq) + H2O(l)  H2(g) + OH-(aq)

• N3-(aq) + H2O(l)  NH3(aq) + 3OH-(aq)
 .          HCl    M   pH   •


• pH= -log[H+]
• pH= -log(0/04)
• pH=
HA(aq) + H2O(l)           H3O+(aq) + A-(aq)


HA(aq)        H+(aq) + A-(aq)

                              -
           [H 3O ][ A ]
      Ka 
               [HA ]
                          -
            [ H ][ A ]
       Ka 
               [ HA ]
HA(aq) + H2O(l)       H3O+(aq) + A-(aq)


                      ]
                  [H3O eqm
 % ionization                100
                   [HA]0
H2SO3(aq)            H+(aq) + HSO3-(aq)
Ka1 = 1.7 x   10-2

HSO3-(aq)            H +(aq)   +   SO32-(aq)

Ka2 = 6.4 x     10-8

  Ka1 > Ka2
 Weak base + H2O      conjugate acid + OH-

NH3(aq) + H2O(l)      NH4+(aq) + OH-(aq)


             [ NH 4  ][OH- ]
        Kb 
                 [ NH3 ]
X-(aq) + H2O(l)         HX(aq) + OH-(aq)


ClO- (aq) + H2 O(l)   HClO(aq) + OH- (aq) Kb = 3.3 x 10-7
           Kb Ka


K w  K a  Kb

pK w  pK a  pK b  14 .00
NH4+(aq) + H2O(l)   NH3(aq) + H3O+(aq)
    O
    C
R       OH
         Lewis
                     .

Lewis acid:          •
                 .

Lewis base:          •
Fe(H2O)63+(aq)        Fe(H2O)5(OH)2+(aq) + H+(aq)


    Ka = 2 x   10-3
 pH




pH
Le Châtelier’s
EO
HX(aq)
HA (aq)       H+(aq) + X--(aq)
                       A (aq)


               -
       [H ][A ]
  Ka 
         [HA ]
                 [HA ]
     [ H ]  K a
                   [A - ]
                          pH


                            [HA ]
 log[ H ]   log K a  log    -
                              [A ]
                      -
                   [A ]
 pH  pK a  log
                  [HA ]
pH
NH3     pH
      NH4Cl
aA + bB            cC + dD

   K eq 
            Cc Dd

            A a Bb
  CaCO3(s)          CaO(s) + CO2(g)

        [CaO]
K eq            [CO 2 ]  constant  [CO 2 ]
       [CaCO3 ]
A- + H3O+  HA + H2O
HA + OH-  A- + H2O
–
–
                    –

HC2H3O2(aq) + NaOH(aq)  C2H3O2-(aq) + H2O(l)
–
–
pH
–
  CaCO3(s)          CaO(s) + CO2(g)

        [CaO]
K eq            [CO 2 ]  constant  [CO 2 ]
       [CaCO3 ]
 The Solubility-Product Constant, Ksp



BaSO4(s)            Ba2+(aq) + SO42-(aq)


    K sp  [Ba 2 ][SO 2- ]
                       4
EOS
Common-Ion Effects

CaF2(s)    Ca 2+(aq)   +   2F-(aq)
  Complex Ion Effects

Ag+(aq)   + 2NH3(aq)    Ag(NH3)2(aq)

              [Ag(NH3 )2 ]
     Kf 
             [Ag  ][ NH ]2
                        3
                     +          -
 AgCl(s)         Ag (aq) + Cl (aq)

 Ag+(aq) + 2NH3(aq)           Ag(NH3)2(aq)

AgCl(s) + 2NH3(aq)       Ag(NH3)2(aq) + Cl-(aq)
   Amphoterism

Al(OH3)(s) +   OH-(aq)   Al(OH)4-(aq)
BaSO4(s)              Ba2+(aq) + SO42-(aq)
• Q = [Ba2+][SO42-]
  • Q < Ksp
  • Q = Ksp
  • Q > Ksp
MdiluteVdilute = MconcentratedVconcentrated

      Mfinal Vfinal = MinitialVinitial
HCl(aq) + NaOH(aq)  H2O(l) + NaCl(aq)

   ionic:
H+(aq) + Cl-(aq) + Na+(aq) + OH-(aq)  H2O(l) +
 Na+(aq) + Cl-(aq)
2HCl(aq) + Na2S(aq)  H2S(g) + 2NaCl(aq)

2H+(aq) + S2-(aq)  H2S(g)

HCl(aq) + NaHCO3(aq)  NaCl(aq) + H2O(l) + CO2(g)
–



    Emf
Oxidation and Reduction

   Ca(s) +2H+(aq)  Ca2+(aq) + H2(g)
Oxidation and Reduction
Mg(s) +2HCl(aq)  MgCl2(aq) + H2(g)


  Fe(s) +Ni2+(aq)  Fe2+(aq) + Ni(s)
Free Energy Change


DG0 = – nFE0


DG < 0

DG > 0

DG = 0               EOS
            Oxidation


Fe( s)  Cu 2 (aq)  Fe 2 (aq)  Cu ( s)
                        Reduction


                                             :Oxidation –

  Fe( s)  Fe 2 (aq)  2e 
                                             :Reduction –



   Cu 2 (aq)  2e   Cu ( s )
                                     o
                                E

2 H   2 e   H2   E o  0.000 V




     Zn 2   2e   Zn
     Cu 2   2e   Cu
     Fe 3  e   Fe 2 
H2

          Pt




     H+
                                 Redox


             2                  2
Fe( s)  Cu (aq)  Fe (aq)  Cu ( s)

             Oxidation


   Fe( s)  Cu 2 (aq)  Fe 2 (aq)  Cu ( s)
                         Reduction
F2 + 2e–  2F–         +2.87
Co3+ + e–  Co2+       +1.81
Au+ + e–  Au          +1.69
                               2Au+ + Cu → Cu2+ +2Au
Ce4+ + e–  Ce3+       +1.61
Br2 + 2e–  2Br–       +1.09
Ag+ + e–  Ag          +0.80
Cu2+ + 2e–  Cu        +0.34
AgCl + e–  Ag + Cl–   +0.22
Sn4+ + 2e–  Sn2+      +0.15
                      Zn + Cu2+  Zn2+ + Cu

anode                                                     cathode
              Zn |   Zn2+   (x M) ||   Cu2+(y   M) | Cu




    Pt | H2(g) (a=1) | H+ (a=1) || Cu2+(0.01M) | Cu


        Hg | Hg2Cl2 | KCl (sat’d) || Fe2+(0.001M) | Pt
‫آند‪ - E‬كاتد‪ = E‬سلول ‪E‬‬
                                 • choose one reaction for reduction
F2 + 2e–  2F–         +2.87
                                 • choose another for oxidation
Co3+ + e–  Co2+       +1.81
Au+ + e–  Au          +1.69   Sn4+ + 2e–  Sn2+
Ce4+ + e–  Ce3+       +1.61   Ce3+  Ce4+ + e–
Br2 + 2e–  2Br–       +1.09   Overall Reaction:
                               Sn4+ + 2Ce3+  Sn 2+ + 2Ce4+
Ag+ + e–  Ag          +0.80
Cu2+ + 2e–  Cu        +0.34
                               Cell potential E:
AgCl + e–  Ag + Cl–   +0.22
                               E = +0.15 - 1.61 = -1.46 V
Sn4+ + 2e–  Sn2+      +0.15
                                V
                          salt bridge
                                                    e
              e
‫اكسيداسيون‬    Zn                               Cu
ANODE              Zn2+                 Cu2+            CATHODE




             Zn + Cu2+  Zn2+ + Cu

             Zn  Zn 2   2e 
             Cu 2   2e   Cu
emf
          
DG  DG  RT ln Q

                  
n
 F E  n F E  RT lnQ

             RT
              
      E E     lnQ
           nF
aA + bB  cC + dD


EE   0                     C  D
                              c
           0.0592 / n  log a b
                                   d


                            A B
          DGo Keq


DGo = RT ln Keq
E  E 0  0.0592 / n  log Q

Ecell  0  E  0.0592 / n  log K
             0




 E  0.0592 / n  log K
   0


         RT             0.0592

 K e   nFE 0
                  10    nE 0
Pt | I– (1.00 M), I2 (1.00 M) || Fe2+ (1.00 M), Fe3+ (1.00 M) | Pt

E0 = 0.771 V - 0.536 V = +0.235 V

                    C                       J
DG  n F E  2 96285      0.235 J   45,348
                   mol                     mol

                               45348 J 
                   DG                 mol 
       ln Keq                                     18.3034
                   RT     8.314    J 
                                            298 K 
                                 K mol 
       Keq  e18.3034  8.89  10 7
       
Fe2+ + 2e– → Fe          -0.44
V2+ + 2e– → V            -1.19

Fe2+ + V → Fe + V2+

Ecell = -0.44 - (-1.19) = +0.75 V
Sn2+ + 2e– → Sn             -0.14
Ag+ + e– → Ag               +0.80

2 Ag+ + Sn → 2 Ag + Sn2+

Ecell = +0.80 - (-0.14) = +0.94 V
  2          –                                       2              –
Cu  aq   2 e  Cu s                 Zn  s   Zn  aq   2 e

             Cu 2aq   Zn  s  Zn 2aq   Cu s


          EE   RT ln aCu aZn 2
                  n F a 2 aZn
                       Cu
EE   RT ln    Zn 2   
                   1.10  0.01285 ln
                                               Zn 2    

        2 F Cu 2
                                    Cu 2             
                        1.00
  E  1.10  0.01285 ln       1.10  0.01285 ln 100
                        0.01
     1.10  0.01285 4.6052   1.041V
               (Weston   )




Saturated CdSO4
    solution



   CdSO4 (s)                     Hg2SO4 (s)



     Cd(Hg) (l)
                                 Hg (l)


                  —          +
                                          Weston

   Cd(Hg) → Cd2+(aq) + 2e–

  Hg2SO4(s) + 2e– → 2 Hg(l) + SO42–(aq)


Cd(Hg) + Hg2SO4(s) → 2 Hg(l) + Cd2+(aq) + SO42–(aq)


Cd(12.5% Hg amalgam) | CdSO4(aq, sat) | Hg2SO4 (s) | Hg(l)
                                                   Weston

                       2
                     a Hg   a        2    a      2
           RT                   Cd             SO 4
 E  E 
      o
                ln
           nF          a Cd a Hg
                                          2 SO 4




   
EE 
      0.0257
                Cu 2
             ln
                            
                          anode 
                                             
         n      Cu 2 
                               
                         cat hode 
                                               
        0.0257 0.001
    0       ln             0.089 V
         2      1.00 
                                         Daniell
 Anode (oxidation)                   Cathode (reduction)
             –ive    salt bridge     +ive
       Zn metal                          Cu metal




                                               CuSO4 (aq)




Zn(s)  Zn2+(aq) + 2e–             Cu2+(aq) + 2e–  Cu(s)
                           :   E˚   •

AgCl (s)  Ag (s) + Cl- (aq)

Ksp (AgCl) = 1.8 × 10-10
                    IR


Ecell = Ecathode – Eanode – EIR
         DG o   nFEo whereF  96,500coul / eq;
         n  no.e  transf erred
                  DG o            nFEo
         ln K           
                   RT               RT
                RT                 0.059
         Eo        ln K                log K
                nF                   n
Nernst equation:
                      RT
    E  E     o
                          ln Q
                      nF
    or
                      0.059
    E  Eo                 log Q (T  298K )
                        n
– Electrolyte
– Anode
– Cathode
Voltaic Cell
                                         2            
                         Zn ( s)  Zn (aq)  2e

     
2NH 4 (aq)  2MnO2 (s)  2e  Mn2O3 (s)  H 2O(l )  2NH3 (aq)
• Alkaline battery




• Lithium-iodine battery
• Lead-acid battery




• Lithium-ion battery
      – Anode:
              
Pb ( s )  HSO4 (aq)  PbSO4 ( s )  H  (aq)  2e 


      – Cathode:
                           
 PbO2 ( s )  3H   HSO4  PbSO4 ( s )  2 H 2O
VI A


 VA



IV A
III A
      IA      II A      III B        IV B    VB       VI B    VII B             VIII B             IB       II B     III A   IV A      VA      VI A      VII A    VIII A
       1                                                                                                                                                   1        2
1     H                                                                                                                                                    H       He
     1.008                                                                                                                                               1.008    4.0026
       3       4                                                                                                       5       6        7        8         9        10
2     Li      Be                                                                                                      B       C        N        O          F       Ne
     6.939   9.0122                                                                                                 10.811   12.011   14.007   15.999   18.998    20.183
      11       12                                                                                                     13      14       15       16         17       18
3    Na       Mg                                                                                                      Al      Si       P        S         Cl       Ar
     22.99   24.312                                                                                                 26.982   28.086   30.974   32.064   35.453    39.948
      19       20        21          22      23       24       25       26       27       28       29       30        31      32       33       34         35       36
4     K       Ca        Sc           Ti      V        Cr      Mn        Fe      Co        Ni       Cu       Zn       Ga      Ge        As       Se        Br       Kr
    39.102   40.08    44.956     47.89      50.942   51.996   54.938   55.847   58.932   58.71    63.54    65.37     69.72   72.59    74.922   78.96     79.909    83.8
      37       38        39          40      41       42       43       44       45       46       47       48        49      50       51       52         53       54
5    Rb       Sr         Y           Zr      Nb      Mo        Tc       Ru       Rh       Pd       Ag      Cd         In      Sn       Sb       Te         I       Xe
    85.468   87.62    88.906    91.224      92.906   95.94     * 98    101.07   102.91   106.42   107.9    112.41   114.82   118.71   121.75   127.61    126.9    131.29
      55       56        57          72      73       74       75       76       77       78       79       80        81      82       83       84         85       86
6    Cs       Ba       **La          Hf      Ta       W       Re       Os         Ir      Pt       Au       Hg        Tl      Pb       Bi       Po        At       Rn
    132.91   137.33   138.91    178.49      180.95   183.85   186.21   190.2    192.22   195.08   196.97   200.29   204.38   207.2    208.98   * 209     * 210    * 222
      87       88        89          104     105      106      107      108      109      110      111      112       113     114      115      116
7     Fr      Ra ***Ac               Rf      Ha       Sg       Ns       Hs       Mt      Uun Uuu Uub                 Uut     Uuq Uup Uuh
     * 223   226.03 227.03       * 261      * 262    * 263    * 262    * 265    * 268    * 269    * 272    * 277     *284     *285   *288     *292
                                                                                                                    Based on symbols used by ACS        S.M.Condren 2003
                                             58       59       60       61       62       63       64       65        66       67     68       69          70       71
    * Designates that **Lanthanum           Ce        Pr       Nd      Pm       Sm        Eu      Gd        Tb       Dy       Ho       Er      Tm         Yb       Lu
    all isotopes are  Series                140.12   140.91   144.24   * 145    150.36   151.96   157.25   158.93   162.51   164.93   167.26   168.93   173.04    174.97
    radioactive                              90       91       92       93       94       95       96       97        98      99       100      101       102      103
                      *** Actinium           Th       Pa       U        Np       Pu      Am       Cm        Bk        Cf      Es      Fm       Md         No        Lr
                      Series                232.04   231.04   238.03   237.05   * 244    * 243    * 247    * 247     * 251   * 252    * 257    * 258     * 259    * 260
    •
–
–
–
–
–
    •
–
–
–
–
–
‫ا‬
NaCl                     KI
  sodium chloride          potassium iodide
Fe2O3                    Mg3N2
  iron(III) oxide          magnesium nitride
N2O4                     SO3
  dinitrogen tetroxide     sulfur trioxide
CaF2(s) + H2SO4(l) →HF(g) + CaSO4(s)



 NaCl(s) + H2SO4(l) →HCl(g) + NaHSO4(s)
     VI A


O2             •
               •
     O2        •
            MnO2
      O22-        O2-               •
                             O 2-


                                    •


2KO2 + 2H2O→ O2+ H2O2+2KOH
                          H2O2   •
2H+ +2SO42-→ H2+ S2O82-


2H2O+ S2O82-→H2O2+ 2H+ +2SO42-
     •
S8

     •
                                    •
        TeO2                 SeO2


                         H2SeO4     •
H2SeO3+ H2O2 → H2SeO4+ H2O


          H6TeO6                    •
VI A
                VA


            ns2 np3     •
                      X3-
                        •
VI A   IV               •


                        •
     VA

VA
N2 + O2 → 2NO
6Li + N2 → 2Li3N
3Mg + N2 → Mg3N2
Mg3N2 + 6H2O → 2NH3 + Mg(OH)2
P-F > P-Cl > P-Br > P-I
     VA

VA
VA


VA
IV A
CO   CO2
  III A

III A
EDTA
EDTA
d
d
d1
d2
d3
d4
d5

								
To top