The "Golden Penny" Demonstration

The "Golden Penny" Demonstration
An Explanation of the Old Experiment and the Rational Design of the New and
Simpler Demonstration
Steven H. Szczeoankiewicz. Joseoh F. Bieron. and Mariusz ~ o z i k '
Canisius College, Buffalo, NY 14208
The demonstration referred to a s "Striking I t Rich" (1) duction potentials of zincate ion on different surfaces due
and "Copper to Silver to Gold" (2), or more commonly as to low-temperature alloy formation, but first we will pre-
the "Golden Penny Experiment" is popular among general sent the explanations proposed in the literature.
chemistry teachers and is described in the two widely used
chemistry texts cited above. Both of these texts, however, Suggested Explanations in the Literature
present a n insufficient or incorrect explanation for the ma- Both of the sources cited above make an attempt to explain
jor part of the experiment. This paper reports a series of the chemistry behind the mysterious reduction of zinc.
electrochemical measurements that lead to a logical expla- Aconcentration cell was proposed as a source of the driv-
nation for this demonstration and to a simplified design ing force for step B by Shakhashiri (2). He found that zinc
that makes it safer. can be deposited on a copper electrode in an electrochemi-
In the popular version of this experiment granular zinc cal cell consisting of a zinc plate in NaOH solution in one
is placed in 3M NaOH solution and heated until the liquid half-cell, and copper in sodium zincate solution in the sec-
boils. A copper penny is then placed in the beaker and the ond half-cell. In this cell, zincate ions are reduced to zinc a t
heating continues. After a short time the copper coin be- the copper cathode and zinc is oxidized to zincate ions a t
comes silvery (zinc deposits on copper). The silvery coin is the zinc anode. The net reaction is driven then by the dif-
subsequently heated in the cold part of a Bunsen burner ference in concentration of zincate ions in the two half
flame and the coin turns golden (1,2). cells. A similar concentration gradient was proposed by
The experiment, a s presented above, consists of three Shakhashiri to exist in this demonstration. Our experi-
separate chemical processes: mental work confirms Shakhashiri's assignment of the re-
Step A. Granular zinc dissolves in NaOH solution, forming a ducing agent (zinc metal), but clearly excludes the concen-
zincate anion, [z~(oH)~]". tration gradient as the driving force for the reaction.
Step B. Zincate ion becomes reduced to metallic zinc on the The Teacher's Guide for reference 1(3)simply states that
surface of the capper penny. the reason for the reduction to zinc taking place is that
Step C. Zinc and capper, when heated in the Bunsen burner zincate ion can react to plate zinc metal on the copper sur-
flame, form brass. face. This explanation does not identify t h e reducing
Of the three chemical processes presented above, steps A agent. In addition, it creates a n impression that the pres-
and C are easy to explain (1,2). ence of zinc complexed by hydroxide ions (zincate) is neces-
In step A metallic zinc dissolves in NaOH solution be- sary for this process to take place. In fact, this convenient
cause of the following reduction potentials: explanation is used by high school teachers when they pre-
sent this experiment to students. However, our electro-
chemical measurements, uide infra, clearly show that com-
plexation of zinc with hydroxide ions is not necessary for
the reduction of zinc to take place.
Therefore, if reaction 1is reversed and combined with re-
action 2, the net reaction 3 takes place a s the result of 0.4 An Explanation Based on the Reduction Potentials
V of the driving force: Determined in This Work
In order to definitely exclude the possibility that copper
itself could be a reducing agent we determined the amount
Step C of this experiment is a typical example of a high- of deposited zinc on the plate and compared it to the
temperature alloy formation and does not require any spe- amount of copper in solution. Both metals were deter-
cial explanation. mined by AAspectroscopy. Copper was measured in the so-
None of the cited references present, however, a satisfac- lution used for zinc deposition, and zinc was determined
tory explanation for step B in the experiment. The ques- . . d. a t e with 1.0 M HC1 solu-
after dieestion from the comer
tion one needs to address is why does zincate anion become tlon (The two solut~onshad cqual \v~lumcxI The molar ra-
reduced to zinc (from +2 oxidation state to O)? What is the o Zn to Cu was found to be more than 20 1 I T ~Irvel
t ~ of P
reducing agent? I t cannot be water, because it is shown of copper was below detection limit by AA.) This clearly
above that water will actually oxidize zinc a t the pH of the excludes copper as a possible reducing agent.
experiment. The same argument excludes hydrogen gas a s Next, we constructed the electrochemical cell similar to
a possible reducing agent. Metallic copper is also ruled out, the cell designed by Shakhashiri, hut consisting of 1 M so-
because copper is a much poorer reducing agent than zinc dium zincate solution in both half cells. See the figure.
a t any pH. Besides, the solution remains colorless, indicat- Note that there is no concentration gradient in the cell.
ing that no oxidation of copper takes place. The voltage in this cell was determined to be 1.1V. There-
We will show below that the reducing agent is zinc itself, fore, a very large driving force exists for the redox reaction
and the driving force is related to the difference in the re- in which zincate is reduced to zinc on copper and the zinc
plate is oxidized to zincate. Zinc indeed does deposit on
'Author to whom correspondence should be directed. copper in this cell when the electrodes are connected by an
386 Journal of Chemical Education

Table 1. Voltages of the Electrochemical Cells
Assembled from the Following Two Half Cells
Separated by a Glass Frit.
Anodc half cea Zn meta n 1 M ha2[Zn(OH)4]
Calhodc haf!cell X (another metal or grapn le) n 1 M Na?[Zn(OHldI
The net reaction Em,. V
An electrochemicalcell used toexplain the chemistry behind theclas-

sical "golden penny" experiment, involving 3M NaOH solution. X=Cu. a1 are indistinguishable. There was no appreciable poten-
Pt. Ag, Fe, Cd and C,,,,,.. tial drop in the cell containing zinc and cadmium elec-
trodes. All of the metals on which we were able to deposit
zinc are known to form alloys with zinc. Cadmium is the
external wire (2 minutes when the solutions are hot, and only metal of those tested in this work that does not form
-1 hour in cold solutions). any intermetallic compounds with zinc (5).
Therefore, we have shown that The nature of the silvery color of the deposit on the sur-
E ( [ Z ~ ( O H ) ~ I-~E?"Z( ~
[ Z~ ~~ () O H ) ~ I=~1.1
/ ZV~ ~ ~(4)
) face of Cu requires further explanation. I n the chemical eq
5 we show the product of the reaction being Znc,, the inter-
and the net reaction for the process of the zinc deposition metallic compound of zinc and copper = brass. However,
on copper is the color of the deposit is silvery. The color becomes golden
ZnZn+ [z~(oH),I" + [z~(oH),I" + Zncm (5) only when the coin is heated i n the flame or when the con-
centration of Zn-containing compound in solution is very
We have independently confirmed this result by measur- small (=0.01 MI. The explanation requires a consideration
ing the potentials of [Zn(OH)412-/Zncuand [Zn(OH)41"/Znz. of various types and colors of known brasses. The color of
versus standard calomel electrode. The difference between brass changes depending on the Zn content. One form, a-
those two measurements was again 1.1V. The subscript in brass, with the zinc content less than 35% is golden in
the symbolism used above identifies the surface on which color, while y-brass with a zinc content of more than 45% is
the reduction takes place. Table 1 presents the results of silvery-gray. Therefore, the meaning of Znc, in eq 5 i s dif-
similar measurements for other surfaces. ferent depending on the duration of the experiment. At the
The measurements presented in Table 1 show that the very beginning i t is the a-brass that forms a t the surface.
reduction potential of the zincate ion is very strongly af- However, as time progresses, owing to the slow diffusion of
fected by the surface on which the reduction takes place. metal atonls at temperamres less than 100'C the content
Zincate being reduced to zinc on copper (or on several other of Zn in the deposit 1s increasing and the consequent losers
surfaces) is much more favorable than zincate be in^ re- e\.ctntuallv become y-t~rass. Therefore, the d)sc:rvt~dcolor of
dnced to 7inr on 7inr. We condudrd that an incrran! in the the depos~t1s silvern This also expta~nswhj the deposition
r d u c t i m potmti:ils is caused tw the fact that zlnc atoms of Zn stops after a short time or idvery sig&cantl~ slowed
diffuse in& the lattice of the more noble metal (or graph- down. The reduction potential of [Zn(OH)41Z-/Znc,(a-brass)
ite) forming a n alloy of zinc and the more noble metal a t i s much larger (close to 1 V) t h a n [Zn(OH)412~Znc&
the surface or a n intercalation compound with graphite. brass), which is approximately 0.01 V. Therefore, the volt-
(The intercalation compounds of zinc with graphite have
age of the cell from the figure drops to almost zero (=I0
been reported in the literature (41.1
mV) when the copper plate becomes silvery. However,
The following two observations supply additional proof
when the y-brass on t h e surface is transformed into a-
that the diffusion rate of zinc is sufficiently high for alloy
formation a t the conditions applied i n the demonstration. brass (by heating i n the flame), the deposition process con-
tinues and the plate becomes silvery again!
1. W h e n the concentration of zinc-containing electrolyte is
lowered to 0.01 M, the copper plate changes color to gold The Rational Design of a Simpler "Golden Penny"
in solution,and the heating in the flame is not necessary Experiment
to visuallv detect an allav Anew electrochemical cell was constructed where IMso-
2 The silwq plntcs ohrninrd from more ronrmtrated solu- lution ofZnClp was substituted for Na2[Zn(OH)41in the fig-
tions hrrorne gold if kept at room temperature for a pm-
longed amount of time ( 2 4 days). ure. The measured voltage was 0.70 V and zinc plated on
copper again (after several hours a t room temperature).
We have been able to plate zinc on graphite and all the Therefore,
metals presented in Table 1,except cadmium. In all cases = 0.70 V
E(znZt(aq)i~nc,)-E"(Zn2+(aq)/Znzn) (5)
the thickness of the zinc layer is very small (less than 0.03
pm a s determined by AA). As the metallic zinc deposits on
the surface of the metal the voltage of the cell drops to al-
most zero. The large drop of the potential is i n fact the best
way to determine that zinc has deposited on the surface, Clearly, there is no need to include a highly corrosive con-
because in many cases the colors of zinc and the other met- centrated NaOH solution in the demonstration. A much
Volume 72 Number 5 Mav 1995 387

The "Golden Penny" Demonstration

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The "Golden Penny" Demonstration

386 Journal of Chemical Education

An electrochemicalcell used toexplain the chemistry behind theclas-

Volume 72 Number 5 Mav 1995 387

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