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DETERMINATION  OF  ELECTRODE  POTENTIALS  

N.  CASTOR  
INSTITUTE  OF  BIOLOGY,  COLLEGE  OF  SCIENCE  
UNIVERSITY  OF  THE  PHILIPPINES  DILIMAN,  QUEZON  CITY  1101,  PHILIPPINES  
DATE  SUBMITTED:  April  24,  2015  
DATE  PERFORMED:  April  17,  2015  
______________________________________________________________________________________________________________________________  

I.  Answers  to  Questions  
1.  Discuss  the  differences  between  galvanic  and  electrolytic  cells.  

A   galvanic   (or   voltaic)   cell   refers   to   a   cell   that   has   a   spontaneous   reaction   occurring.   This   is   due   to   the   △G   in  
Equation  1  to  be  negative.  It  must  be  noted  that  z  and  F  are  always  positive  numbers,  therefore  for  △G  to  be  
negative,   Ecell   should   be   positive.   According   to   Equation   2,   this   means   that   the   cathode   has   a   higher   reduction  
potential  than  the  anode.  This  contributes  to  the  spontaneity  of  the  galvanic  cell.  Another  thing  to  take  into  
consideration  is  the  conversion  of  energy.  Since  the  reaction  is  the  transfer  of  electrons  from  one  half-­‐cell  to  
the   other,   and   taking   into   account   the   spontaneity   of   the   reaction,   it   can   be   said   that   chemical   energy   is  
converted  into  electrical  energy,  that  is  the  transfer  of  electrons  is  due  to  the  presence  of  the  redox  reaction.  
These  electrons  are  provided  by  the  species  that  is  undergoing  oxidation.  [1][2][3]  
 

 

 

 

 

 

 

 

 

                     

 

ΔG = −zFE ocell
E ocell = E ocathode − E oanode

(1)  
(2)  

The   electrolytic   cell,   on   the   other   hand,   is   a   cell   wherein   the   △G   in   Equation   1   is   positive,   denoting   a   non-­‐
spontaneous  reaction.  This  means  that  the  Ecell  of  the  cathode  is  smaller  than  the  anode’s  and  therefore  has  a  
smaller   reduction   potential.   In   order   to   have   a   reaction,   the   electrolytic   cell   has   to   be   charged   with   an   outside  
source,   e.g.   a   battery.   In   the   electrolytic   cell,   unlike   the   galvanic   cell,   electrical   energy   is   converted   to   chemical  
energy,  that  is,  the  reaction  occurs  thanks  to  the  Ylow  of  electrons.  These  electrons  are  provided  by  the  battery  
that  is  connected.  [1][2]  
Another  difference  between  galvanic  and  electrolytic  cells  is  the  set  up  itself.  In  a  galvanic  cell,  the  species  are  
separated,  connected  by  the  wire  and  a  salt  bridge,  while  in  the  electrolytic  cell,  the  species  are  in  the  same  
beaker.  [2]  
The  last  difference  between  galvanic  and  electrolytic  cells  is  the  charge  of  the  electrodes.  In  a  galvanic  cell,  the  
anode   has   a   negative   charge   due   to   the   oxidation   happening   in   the   beaker   that   contains   the   negative  
electrode.   The   cathode   therefore   has   a   positive   charge   as   it   is   contained   in   the   beaker   of   the   reduction  
reaction.   However,   in   an   electrolytic   cell,   the   charges   are   reversed,   that   is,   the   anode   is   positive   and   the  
cathode   is   negative.   This   is   because   the   assignment   of   anode   and   cathode   to   the   electrode   is   not   based   on   the  
charge,  but  the  reaction  that  occurs  on  it.  [3]  

1

044 0..   Half-­‐cell Voltmeter  Reading  (V) Zn2+|Zn 0.  The  Eored  of  each  half-­cell  and  their  literature  values.   Half-­‐cell Standard  Reduction   Potential  Experimental   Value  (V) Standard  Reduction   Potential  Book  Value*  (V) %  error Zn2+|Zn -­‐0.79 0.   Based   on   your   observations.   Table  1.  while  the  half  reaction  occurring  at   the  cathode  is  a  reduction  half  reaction.  along  with  their  %  error.   what   are   the   half   reactions   which   occur   at   the   anode   and   cathode   during  the  electrolysis?   During  electrolysis.61 -­‐0.  which  Eored   is  known.  Although  it  was  not  seen  in  the  experiment  conducted.  the  expected   results  were  brown  gas  bubbles  coming  from  the  anode  [4].464 Br-­‐|Br2|C 0.  whichever  electrode  it  is  assigned  to  in  the  set-­‐up.  The  Eored  of  the  unassigned   electrode  can  then  be  found.45 Br-­‐|Br2|C 0.   found   in   table   1   below.  The  voltmeter  reading    is  substituted  to  the  Eocell  and  the  Eored  of  Cu2+/ Cu  to  either  cathode  or  anode.763 20.20 3.   Table  2  below  shows  the  Eored  of  the  half-­‐cells  and  their  literature  values.   This   can   be   seen   in   Equation   3.   Table  2.   it   can   be   noted   that   Bromide   ions   donate   their   electrons  to  the  anode  to  produce  Bromine  molecules  in  aqueous  form.95 Fe3+|Fe2+|C 0.80 *taken  from  Fundamentals  of  Analytical  Chemistry  by  Skoog.  By   using   Equation   2.               −                             2Br(aq) → Br2(aq) + 2e − (3)   2 .2.   4.  This  indicates  an  oxidation  half  reaction  taking   place.  The  measured  Ecell  values.  the  half  reaction  that  occur  at  the  anode  is  oxidation.  et  al.  What  is  the  measured  value  of  Ecell  for  each  cell  and  its  relevance  to  the  Eored  for  the  iron  half-­cell  and   halogen  half-­cells?   The   measured   Ecell   values.22 I-­‐|I2|C 0.024 1.087 97.77 I-­‐|I2|C 0.  2004.Compare  the  calculated  Eored  for  each  half-­cell  with  their  literature  value.   the   experimenters   can   calculate   the   standard   reduction   potential   of   the   half-­‐cells   by   simply   substituting  the  values  to  the  equation.   give   the   experimenters   an   idea   of   what   the   Eored   of   the   different  half-­‐cells  would  be.771 2.05 Fe3+|Fe2+|C 0.   In   this   equation.  This  is  thanks  to  the  presence  of  a  reference  electrode.615 92.

  Br-­‐   becomes   the   reducing   agent   of   H2O   at   the   cathode.  then  △G  is  positive.   The   graphite   electrodes   used   in   the   experiment   were   mechanical   pencil   reYills.  S.   This   would   theoretically   create   effervescence   as   the   H2O   becomes   H2   gas.   Their   different   composition  from  the  pure  graphite  electrodes  that  were  required  may  have  caused  an  indeterminate  effect   on   the   calculated   parameters.   meaning   a   spontaneous   reaction.While   this   is   happening   at   the   anode.   Another   possible   source   of   error   would   be   a   malfunctioning   battery.   Based   on   the   same   values.   The   graphite   electrodes   may   have   not   been   working   right   as   they   may   have   not   been   the   ones   that   were   needed.  10th  ed.  Toronto:  Pearson   Canada.   [2]  Analytic  Chemistry  Academic  Group.   This   is   the   copper   undergoing   a   reduction   reaction   to   form   solid   copper.  the  calculated  parameters  would  decrease.  there  will  be  no   reaction.   the   most   effective   reducing  agent  is  actually  bromine  as  it  has  the  highest  standard  reduction  potential  among  the  four  reagents.  what  are  the  most  effective  reducing  and  oxidizing  agents?   Based   on   the   calculated   values.  as  the  measured  values  would  not  be  accurate.   The   same   should   happen   at   the   Iodine   half   cell.  Student  solutions  manual:  Fundamentals  of  analytical  chemistry.   if   Ecell   is   positive.   If   the   battery   is   not   working   at   the   voltage   required..  Its  low  standard  reduction  potential  means  it  prefers  to  undergo   oxidation  more  than  to  reduction.   6.   However.   where   the   Iodide   ions   get   oxidized   to   Iodine   to   form   tri-­‐iodide   exhibiting   a   yellow   aqueous   form.   An   electrolytic  cell  requires  electrical  energy  to  have  the  reaction.   Like   the   Yirst   set   of   electrolytic   set-­‐ups.   5.  9th  edition.   the   most   effective   oxidizing   agent   is   iron.   then   △G   is   negative.   More   importantly.  D.  If  the  battery  is  not  working.  2013  Version.   This   happens   in   both   the   bromine   and   iodine   set-­‐ups.  Are  values  of  standard  reduction  potentials  helpful  in  determining  the  spontaneity  of  a  reaction?   The  values  of  standard  reduction  potentials  can  be  used  in  calculating  the  spontaneity  of  a  reaction  simply  by   relating  the  Gibb’s  Free  Energy  equation  and  the  standard  reduction  potentials.   Furthermore.  [1][3]   7.  This  is  because  the  current  supplied  in  electrolysis  is  in   the   numerator   of   Faraday’s   law.  SOURCES   [1]  Crouch.  Print.   A   decrease   in   this   value   would   cause   the   overall   mass   to   decrease   as   well.   hence   the   calculated   parameters   would   be   affected.  Quezon  City:   University  of  the  Philippines.  Their  relationship  is  shown  in   equation   1.  Institute  of  Chemistry.   One   is   the   set-­‐up   itself.   Based   on   the   standard   reduction   potential   book   values.   the   other   is   negative.  exhibiting  effervescence.  R.  In  the  other  electrolytic  cell.   if   Ecell   is   negative.   3 .   is   zinc.  Analytical  Chemistry  Laboratory  Manual.   Belmont.   while   the   H2O  is  reduced  to  H2  gas.   the   most   effective   reducing   agent.   having   the   highest   standard   reduction   potential   experimental   value.  Based  on  the  calculated  values.   This   would   result   in   indeterminate  errors.   It   has   the   lowest   standard   reduction   potential  both  experimental  and  book  value.  CA:  Brooks/Cole  Pub.  General  chemistry:  Principles  and  modern  applications.   II.   [3]  Petrucci.   Another   possible   source   of   error   would   be   a   deYicient   voltmeter   or   ammeter.  2012.  (2011).  (2014).   meaning   if   one   is   positive.   it   is   important   to   note   that   the   %   error   in   some   of   the   trials   calls   on   further   consideration.  a  reddish  solid  forms  at  the   cathode.  What  are  the  possible  sources  of  errors  and  their  effect  on  the  calculated  parameters?   The   high   %   error   exhibited   by   the   electrolytic   cell   can   be   attributed   to   a   lot   of   factors.   the   iodine   and   bromine   form   their   respective  oxidation  products.  &  Skoog.  meaning  a  non-­‐spontaneous  reaction.   Notice   that   their   signs   are   inverted.

22 I-­‐|I2|C C|I2|I-­‐||Cu2+|Cu Cu|Cu2+ Graphite Cu|Cu2+ 0.087 97.7  mA 60 Half-­‐cell Cell  Notation Positive   Electrode   (Cathode) Negative   Electrode   (Anode) Reference   Electrode Voltmeter   Reading Br-­‐|Br2|C C|Br2|Br-­‐||Cu2+| Cu Cu|Cu2+ Graphite Cu|Cu2+ 0.77 I-­‐|I2|C I2  +  2e-­‐  -­‐>  2I-­‐ 0.).20 Table  5.  (n.771 2.044 0.05 Fe3+|Fe2+|C Fe3+  +  e-­‐  -­‐>  Fe2+ 0.80 4 .6  mA 60 I-­‐|I2|C Graphite Graphite 18.79 0.  Retrieved  April  22.d.uk/bitesize/ standard/chemistry/propertiesofsubstances/conduction/revision/5/   III.61 -­‐0.464 Br-­‐|Br2|C Br2  +  2e-­‐  -­‐>  2Br-­‐ 0.024 1.45  V Table  4.  Electrolytic  Cell   Half-­‐cell Observations Current  (mA) Time  (s) Anode Cathode Br-­‐|Br2|C Graphite Graphite 18.615 92.  from  http://www.[4]  Electrolytes  and  electrolysis.bbc.  Galvanic  Cell   Half-­‐cell Cell  Notation Positive   Electrode   (Cathode) Negative   Electrode   (Anode) Reference   Electrode Voltmeter   Reading Zn2+|Zn Zn2+|Zn||Cu2+| Cu Cu|Cu2+ Zn|Zn2+ Cu|Cu2+ 0.  2015.  Determination  of  Standard  Reduction  Potentials   Half-­‐cell Half-­‐Reaction Standard  Reduction   Standard  Reduction   Potential   Potential  Book   Experimental  Value   Value*  (V) (V) %  error Zn2+|Zn Zn2+  +  2e-­‐  -­‐>  Zn2 -­‐0.  Reported  Values   Table  3.763 20.95  V Fe3+|Fe2+|C Cu|Cu2+||  Fe3+| Fe2+|C Graphite Cu|Cu2+ Cu|Cu2+ 0.co.

316 = E Br.771 x 100 % = 2.22 + ⎜ x log 5.01 L − 2 x ⎜⎝ Fx 2 x (Total moles Br − − 2 x moles Br2 ) x E cell = E ocell − 0.01 L ⎛ ⎛ 0.95 = 0.34 − 0.78x10 −4 ⎜⎝ 2 ) 2 ⎞ ⎟ = E cell = 0.024V 5 .988x10 M ⎜⎝ 1 M x 0.01 L = [Br ] = 9.34 − E oZn|Zn2+ = −0.0186 A x 60 s x ⎞ ⎞ 1 − −1 ⎟⎠ ⎟⎠ x 0.|Br 2 = 0.  Sample  Working  Calculations   Calculation  of  Eored  of  Zn2+|Zn   E ocell = E ocathode − E oanode 0.61 Calculation  of  Eored  of  Fe3+|Fe2+|C   E ocell = E ocathode − E oanode 0.0592 9.0592 logQ z ( ⎛ 0.|Br 2 0.988x10 −1 0.79 0.01 L 1 = [Br − ] 0.464 % Calculation  of  Eored  of  Br-­|Br2|C   Ixt 1 x = [Br2 ] Fxz L 0.45 = E oFe3+ |Fe2+ − 0.0186 A x 60 s 1 x = [Br2 ] = 5.78x10 −4 M Fx 2 0.79 %  error   theoretical − exp erimental x 100 % = % error theoretical 0.316V ⎟⎠ E cell = E Cu|Cu2+ − E Br.34 = 0.771− 0.IV.

0187 A x 60 s 1 x = [I2 ] = 5.81x10 −4 M Fx 2 0.0187 A x 60 s x ⎞ ⎞ 1 − −1 ⎟⎠ ⎟⎠ x 0.988x10 −1 0.0443V 6 .0592 logQ z ( ⎛ 0.01 L = [I ] = 9.988x10 M ⎜⎝ 1 M x 0.78x10 −4 ⎜⎝ 2 ) 2 ⎞ ⎟ = E cell = 0.Calculation  of  Eored  of  I-­|I2|C   Ixt 1 x = [I2 ] Fxz L 0.0592 9.01 L ⎛ ⎛ 0.01 L − 2 x ⎜⎝ Fx 2 x (Total moles I− − 2 x moles I2 ) x E cell = E ocell − 0.22 + ⎜ log 5.296 = E I.01 L 1 = [I− ] 0.|I2 = 0.|I2 0.296V ⎟⎠ E cell = E Cu|Cu2+ − E I.34 − 0.

45 0.763 20.044259205764452 =E(I)cell-­‐E(Cu) Theoretical %error Zn -­‐0.808 2 0.771 2.  Appendix Calculations Cu2+/Cu  Eo 0.0524246395806 =(theoretical−experimental)÷theoretical×100 Fe 0.009988433435249 0.00000581437529149609 0.01  L Nernst Voltmeter  reading Eo  Brcell 0.01L moles   electrolyzed Molarity Br2 0.0592÷num  of  e)×LOG(([I-­‐]×[I-­‐])÷[I2])) Eo  Br 0.95 -­‐0.998837124941701 =remaining  moles  of  H-­‐  x  0.61 =E(Cu)−Voltmeter  rdg Fe Graphite Cu 0.0005783282375498 I2 0.087 97.9988433435249 0.774598225119 =(theoretical−experimental)÷theoretical×100 I 0.20 0.615 92.22 0.00998837124941701 =1M×0.V.0005814375291496 Br-­ I-­ remaining  
 moles  of  H-­ 0.00147568844898171 0.00000578328237549878 0.8033811765119 =(theoretical−experimental)÷theoretical×100 7 .0187 60 253.34 Galvanic  cells Cathode Anode Voltmeter  rdg Ecell Zn Cu Zn 0.0186 60 159.000924214789863709 0.46433203631647 =(theoretical−experimental)÷theoretical×100 Br 1.295740794235548 =voltmeter  rdg+((0.79 =Voltmeter  rdg+E(Cu) Electrolytic  
 cells Current  (A) time Molar  mass number  of   electrons mass   electrolyzed Formula given given given given =current  x   =mass   =moles   time  x  molar   electrolyzed  /   electrolyzed/ mass  /  (  F  x  z) molar  mass 0.01L−(moles  electrolyzed×2) [H-­] 0.8 2 0.0241901172929569 =E(Br)cell-­‐E(Cu) Eo  I 0.0592÷num  of  e)×LOG(([Br-­‐]×[Br-­‐])÷[Br2])) Eo  Icell 0.315809882707043 =voltmeter  rdg+((0.