_—__’—
.Fd
-_—’
__’_’—
___—
______d
’4—
_'_—.——
___‘_—_—
_____—
—_’—.
'—._-
_————
__——
_—_‘——
___—__d
‘_———
—_’——
'_——
’—
—_'——-
fl.
__—_.
’4
___'——
.___———
_—__—-
_'_4—
__—_J—
——’
,—_"
______—_-
#—
-___’——

 

TH .

ABSORPTION OF HYDROGEN BY
ELECTROLYTIC NICKEL

THESIS FOR THE DEGREE OF M. S.

Alfred Clark
1932

 

 

 

 

 

Adsorption of Hydrogen by Electrolytic Nickel

A Thesis Submitted to the Faculty
of

Michigan state College

In Pei-tit]. Fulfillment of the Requirements
for

the degnee of Master of Science

Deportnent of Chemistry

by

Alfred Clark

my, 1932.

THREE OF CONTENTS

Introduction

Encories

Apporctus and.natericls
Procedure

Dot.

Calculstions

Drusflmg

Photogrsyh

Discussion

Summary

9463)-

18

The Adsorption of mogen by Electrolytic Nickel

Introduction

The physical and chemical preperties of metals are effected
by the crystalline structure. x-ray studies in recent years sho' that
the structure of metals deposited electrolytically varies with the
amount of hydrogen co-deposited. Whether or not such results can be
attributed to the gas which is held by the crystals or to a different
structure caused by the presence of a g a film on the metal surface
during the formation of the crystals is a preposition open to question.

Ii'his investigation is limited to the study of the quantity of
hydrOgen held by electrolytic nickel together with observations on the
factors which effect the amount of gas adsorbed and the magnitude of
the forces of adsorption.

It has been the usual practice until quite recently to de-
posit nichsl from acid solutions of 5.2 - 6.0 pH. It was believed
that a more acid solution would permit the evolution of hydrogen and
thus cause the nickel to be more brittle. In this connection Phillips
(Trans. Am. Elect. Chem. 8%.. L11. 393, 1931) has shown that nickel
deposited from solutions of greater acidity may be rather soft ...
at least not more brittle than nickel from solutions ranging from a pH
of 5.2 - 6.0. It sears from the work of Phillips that the temperature
is a more important factor than acidity in the determination of the

hardness of a deposit.

2.

Theories

Benton and White (J.A.S.S. 52, 2325, 1930) have given evi-
dence for assuming two distinct types of adsorption of hydrogen upon
nickel: Phylical adsorption prevalent at very low temperatures and
decreasing rapidly from -210 to ~18?» deg. 0., until at higher temp-
eratures this type of adsorption is entirely superceded by chemical
or activated adsorption. The physical or "secondary” type of ad-
sorption as it is sometimes called involves only the hydrogen molecules
whereas in "primary" or chemical adsorption, the molecules suffer
an activation or even complete dissociation.

Another type of retention of hydrogen by nickel is the dif-
fussion of hydrogen through the nickel. This is not a surface phen-
omena, and is comparable to a process of solution. The amount of
hydrogen dissolved in nickel is of mmh lower order than that physio-
ally adsorbed. Sieverts (Z. Physik. Chem. 60, 129, 1907; 68, 115,
1910; Ber. 42, 538, 1909; 43, 893, 1910; 4.5, 221 and 2576, 1912) has
detemined the solubility of several gases in the more cannon metals.
His values for the solubility of hydrogen in nickel are as follows;
it 764 m. of mercury md at a temperature of 9230 0.. 2.63 cc. of
hydrogen were dissolved in 26.97 gms of nickel, whereas at the same
temperature and a pressure of 129 m. the solubility had decreased
to 0.98 cc. At 822° 0. and 764. me. pressure~ 93.80;“. of hydrogen ;
were dissolved and this value decreases to 0.50 cc. at the same temp-
erature and a pressure of 52 m. From all of his data on the solution
of hydrogen in nickel, Sieverts deduced that the amount dissolved varied

as the square root of the pressure. He concluded also that the amount

3.
of nickel surface exposed did not effect the amount of hydrogen dis-
solved, the amount depending on the weight of the sample. It is
evident on this score than that the hydrogen was not being adsorbed
at these temperatures.

Sieverts gives the following smary in regards to the

 

solubility of various gases in certain metals:
HitrOgen: Not dissolved by metals, forms nitrides
with aluminum md iron.

Carbon dioxide: insoluble in copper.

 

Oxygen: soluble in molten silver.

Sulphur dioxide: soluble in molten copper.

 

HydrOgen: soluble in copper, iron, nickel, palladium;
insoluble in cadmium zinc, lead, bismuth,
tin, antimony, silver and gold.
Mayer and Altmayer (Ber. 41, 3063-74, Sept.) take issue
with Sieverts on the results which he obtained on nickel, stating
that Sieverts did not allow time enough for canplete adsorption.
According to Sieverts, the volume of hydrogen taken by by 1 volume
ofnickel at 350° C. and 1 atmosphere is 2 volumes. Mayer and Altmayer
report 5.5 to 50 volumes of hydrogen per 1 volume of nickel under the
same conditions of temperature and pressure. In both cases the nickel
was obtained by the reduction from the oxide, Mayer and Altmayer
state that the adsorption of hydrogen on nickel is directly proportional
to the pressure, thus obeying Henry's Law.
Kehlenberg and French (Trans. Am. Elect. Chem. Soc. LIV. 165,
1928) have shown that there is a correlation between the lowering of the
potential of a metal electrode when gas is bubbled through the electro-

lyte and the adsorptive power of the metal for the gas in question. The

4.
greater the adsorptive power of the metal the greater the lowering of
potential. Nickel shows a drop superceded only by that of palladiun
and platinum.

Clausthal (1361:. Phys. Ges.. 1005-22, 1911) carried out some
work on the adsorption of hydrogen by various metals at very low temp-
eratures. From his experimental results he concluded that the amount
of adsorbed gas is conditicned by solution and a surface condensation.

Much contradictim exists in data published on the affinity
of metals for gases, particularly in the case of adsorption rather than
in the case of solubility, where the state of division of the metal,
that is, the amount of surface exposed plays so important a role. There
is also great confusion as to which of the three types of retention;
physical, chemical or solution are taking place under certain conditions.

The adsorption of gases on metals appears to be a special case
of adsorption of gases on solids, and most of the comnon formulas for
such adsorption do not hold even approximately in their case. The amounts
of gases adsorbed on metals are all of very low order. Perhaps no gen-
eral law of adsorption of gases on solids is possible, for as Langmuir
states, the aspects of adsorption may differ greatly from case to case
in accordance with the variation in atomic structure and in the kind and
distribution of forces in the solid surfaces.

The mount of adsorption of gases on the surfaces of metals
undergoing a process of electrodeposition, it must be admitted, is a
special case of the adsorption of gases upon metals. And even though
the some laws, whatever they may be, apply; the conditions such as sur-
face area, surrounding media, and surface forces, are so peculiarly char-

acteristic that entirely different results may be expected. In the process

5.
of electrodeposition of a metal, the integral surface area must be ex-

ceedingly large, dependent on the size of the individual nuclei deposited.
Apparatus and Materials

The apparatus used is show in Drawing 1 and also in the photo-
graph. It is entirely of glass and cmsists of a tube (1) wherein the
metal is placed, a drying bulb (B) to take up the water vapor adsorbed
by the nickel, a manometer (C) for measuring chmges in pressure due to
the gas evolved from the metal. ll'he rest of the apparatus is used in
purifying the nitrogen which is used as in inert atmsphere, and con-
siste of a Tube (D) containing a capper gauze heated by a nichrome wire
coil for the purpose of taking the oxygen out of the nitrogen, and a
tube (E) to which a drying bulb is attached. The nitrogen can be intro-
duced into the main system at will through the two-way stop-cock (P).

1 Bywao Cenco pump was used to produce a vaccumn. (0) is an electric
heating unit for driving the gas from the metal , and (H) a theme-couple
for measuring the temperature of the unit. Mercury levels were read with
a cathetometer to .05 m. The nickel deposit sealed in a small tube was
introduced into the vaccunn by breaking the tube with an iron weight
lifted by an electromagnet (I).

Composition of the nickel electroyteg'

The same solution was used throughout the entire experiment
and the pH successively lowered by the addition of sulphuric acid. The
composition was as folloes:

140 gas. of nickel sulphate per liter.

15 gms. of Boric Acid per liter.

15 gms. of Ammonium Sulphate per liter.

6.

Current densities were measured with a millimeter in the
electrical circuit.

DH measurements were made with the new type Hellige Com-
parator, using brom-cresol purple and thymol blue standard color discs
and indicator solutions.

Nitrogen:

'i'he comercial gas supplied in tanks was used and purified
as described.
Drying Agent:

Phosphorus pentoxide was foumi to be a such more rapid dry-
ing agent than magnesium perchlorate, counonly known as anhydrous.

The latter was used throughout the work.

7.

Procedure

The nickel was deposited upon steel plates one square
dosimeter in area, ad the deposit peeled from them easily and
dried at room temperature. The nickel deposit is placed in a small
tube, scaled and placed with a soft iron weight in a larger tube.
This larger tube is sealed to the apparatus at (A). The system is
then evacuated at J aid sealed off from the pump. Stop-cock (F)
is opened to admit nitrogen into the main system enough being ad-
mitted to give a pressure of about 100 m., and the stop-cock
closed. The tube containing the metal is broken by the iron weight
lifted by the electromagnet. The manometer levels are read, and
the metal then heated to about 500° c. for thirty minutes. The
system is allowed to cool, mercury levels again noted, and enough
mercury withdrawn from the manometer through the stop-cock (K) to
bring about the same difference in. levels as prior to the heating.

One arm of the monster is accurately calibrated in
cubic centimeters, and the difference in the mercury levels of this
arm before and after heating and adjustment give the volume of the
gas expelled from the metal. Tho barometric pressure is taken and
the gas values converted to standard conditions. The metal is
weighed after the run.

The nitrogen is purified in the following manner: With
stop-cock (3’) open, the system is evacuated at (1.) and sealed off

frm the pulp. Stop-cock (F) is closed and nitrogen admitted until

8.
the pressure is approximately atnn spheric as shown by the gauge (M).
.We gas is retained here in the presence of the heated copper gauze
for fifteen minutes. Stop-cock (F) is then Opened, part of the ni-
trogen rushing into (E). (F) is closed and the gas allowed to remain
in (E) for fifteen minutes after which time it is ready to be intro-
duced into the main system.

The copper gauze is reduced at intervals by exposure mile
hot, to methyl alcohol vapors.

The calibration of the manometer arm was carried out by
weighing water drawn out at 2 co. intervals, and then checking against
a standardised burrette.

Nitrogen was introduced into the apparatus in order to bring
the mercury levels to such a position that mercury on be withdrawn
without exceeding the limits of the manometer. Oxygen was not used
because of the oaralyric action of nickel upon hydrogen and ongen to

form water vapor.

 

 

um..." mono. «0.2. v.3 a .30.: 35.3 flange
2....” «3o. 3.? a.” m mad.» §.Na «3.3 82”.:
not" mom a. 3.: v.3. a «35 3a.? 313” 39.2.
.3. No.3. mm.n~. noun a 31.3. owns: Hfln.n.n 0023.
mm. .33. No.2. aim a Mom; 3.5.9.. 93.: 25.2.
00.0 3.3. No.2. a.” a 03.3 03.2. 30.3 93.3.
8.0 memo. 3.0a aim a 2.9.3 mange 2b.“: «8.2.
8.0 5.80. 3.: fun .n «3.3 3.0.2. «3.3 "3.2.
god—3a . a a . meanes- es.”

H3. .5 H Ho . amend . shops a « Manson nevus“ masses chemo...

\MMJJ H pawns? M 333083 N Lennon. H N 5&2?! H nacho." nope—395” 326” 93865:

 

m6 In as condoned :0»an so even

10.

 

so.n

 

 

dbflmo Oflodh koNN m @NNsNH flflflafih Ohmonfl “Hmobh
mmod Quads Hmanh hoNN m DNHQNH flflwoflfi DwnoOH «@mohb
whoa hHmNa @nanh moNN h «Ahead Dhfiomp “finchn nNHamb
«Dad Nacho Hooflb moNN b meoHH Ninanb hdkood “@9055
Dead mhflna hmanb 50““ 5 NDQoOH canofih flnoofifl OHhamb
omsH "and. QNSVR 00““ m NGOQHH Omflavfi Nflflohfi onwabh
.Qhad nfldba onofik moNN 0 Hddom Hanonh Hnfloflfl Hmnomh
Hood «can. Omoflfi new“ 0 QdNaHH an00§ anmovfl ommomh
fined knows Hdavs boflfl n OOQODH haoamb mOHoOH Duoobb
nmaH WNHmo No.05 hoflN n «QHQHH QNNoflh “@QoOH mflfiofih
oped “duos omens moNN a Hmhafld nonanb Humahd madcap
mfiad ammo. Anods maflN n Ommoflfl DODO¢8 anQOH Ofimabk
a ”one; rel . Juneau “ - e wiflttshec e8 . . I
Hounds .5 a he a 02:95 . shops a . Epsom no»: . massed muons.»
\Nfl .e.o H «swash H unwoaonsm H nuance H «Ic\snnl H cached «39.63 H nacho." nova-83

 

a...” an as condoned among no «can

11.

 

. on.” some. en.sa e.«« e ooe.en oen.me onm.ma one.nm
mn.H coho. 00.05 0.Nu h flonaflfl 000.05 an.0H nnflomm
ob.H NHmm. on.is 5.NN h H0H9¢H H09.0b Hflmomd Ham.dm V
00.0 bmmm. «5.05 h.NN H www.md «ufl.wm www.md «an.mm
00.0 000m. Nh.nh new“ H nh¢.0N “00.n0 nb¢.0N unmonm
00.0 hmonofl Hmoeh Daflm H aflmomd HN§.00 0N9.mH HN§.00
«5.6 «naflod nu.¢h b.NN n Hmo.«d nrn.nb HN0.0H .nom.00
0H.~ 05¢».H H00¢s h.NN a 000.0 Ohm.Hb 000.0H nNm.d0
n¢.n 0050. u0.nh b.flN m ammond 0H¢.on MHN.0H maeodo
00.N 0050.H Ghana O.nm m 00b.m 000.nh 0N0.0H non.m0
00.d nflam. amonh ¢.NN n N00.¢H 0H0.hr «00.0N onm.n0

n00.~ anacow 00.05 haw“ n 00H.nn 0H0.mh 000.0H DQO.H0
Oood «N00. 00.05 boflu n 000.0H nn¢.00 m00.Ha Ddoodm

H332 . .0 £8 a u may en. «

nomads .5 a no ens-none. cusps « . 39sec norms a Masada cacao;

\um .06 . “Emacs « nonosog Incense . «5\uans H 323 nope-6g « amoeba usages:

 

a

a.» an a. seemeeeq dumeueam as seen

12.
Calculations:
The calculations are very simple. The following formula
express the cubic centimeters of hydrogen per gram of nickel at NgTzP:
x = 27Sxp'x X'
760 x T w
Where X is the mount of hydrogen adsorbed, p' is the pressure in run.
during the run, and w is the weight of the nickel sample.

A sample calculation follows:

Difference in levels before heating 62.805 om.
Difference in levels after heating 62.905 om.
Lowering in height of the mercurylevels 5.835 cm.
Average Length of Mometer Arm per 00 volume 1.03 can.

Volume of gas at 738.6 3 Bar. Press. - 629.05 = 109.55 cm. is

z I 5.835
"'1'"?!-

0
Temperature 3 22.7' 0.
Weight of sample 3 1.0778 gm.
00 of hydrogen per gram of nickel corrected to NngP: 3'-

273 x 2 x 5.835 x 109.55

: l 503 cc of nickel
750 x 1.03 x 295.7 x 1.0778 ‘ hm

 

 

ul-i.
C
.

’—
fl
—‘

 

t‘.
C.

""Q-U'd-P a. -1

15.
Discussion

It will be observed on looking at the table of data that the
mount of hydrogen adsorbed by the nickel is roughly constant at most
current densities and rh's. The results could not as a rule be ex.-
actly duplicated, due no doubt to the changing conditions of the electro-
1yte upon continued electrolysis. However, the values lie well within
a range of 1/2 cc. The amount of gas adsorbed is logically dependent to
some extent on the amount evolved at the cathoue, and indirectly dependent
upon the current density and the Ph in so much as these two preperties
effect the ratio of the amount of gas adsorbed to the nickel deposited.
Beyond a certain point, however, an increase in the amount of hydrogen
evolved per unit amount of nickel deposited seems to have no effect upon
the amount of hydrogen adsorbed. This may be explained as follows;

In the formula, a = 191/ n. expressing the variation in the amount
of adsorption, a, with pressure p, k and n being constants characteristic
of the adsorbent, when the pressure has reached a certain value, adsorp-
tion does not increase, the parabolic curve flattening out into a line
practically parallel to the abscissa. It is assumed that at low pressures
the number of gas particles are not sufficiently great in number to entirety
cover the surface of the adsorbent, thus maximum adsorption does not take
place. As the pressure increases, the amber of particles of gas present
per unit volume increases, and at some definite pressure the adsorbent may
becane entirely covered with the gas particles thus bringing about maximum
adsorption. Further increase in pressure will cause no increase in ad-
sorption. This is comparable to the case of adsorption during electro-

deposition. When the amount of gassing is low enough so that the surface

(s

16.

of the nickel is not completely covered then.manimum adsorption.will
not take place. By lowering the pH or increasing the amount of current,
-that is, increasing the amount of gassing, a point will be reached where
the gas will completely cover the surface of the metal and further ins
creasing of current density or lowering of the pH will not increase the
amount of adsorption. In this type of adsorption.then at any constant
pH, the current density plays the same role as the pressure in the above
formula. Thus it is seen from the data that at l ampere per square
decimeter, and a pH of 2.8, no appreciable quantity of hydrogen is ad-
sorbed, whereas at 3 amperes per square decimeter 1.5 cc. per gram are
adsorbed, which is the average maximum amount adsorbed. Thus somewhere
between 1 and 5 amperes is the value of the current density which will
just cause maximum adsorption. Now by determining the current efficiencies
in this range, the value for the rate of evolution of hydrogen which will
Just cause maximum adsorption may be obtained, i.e. the amount of gas
which will just completely cover the surface of the nickel.

The time of deposition has no appreciable effect on the amount
of gas adsorbed, so that the rate of diffusion.may be considered.negligible.

The hydrogen is held upon the nickel quite tenaciously; in fact a

sample of nickel may be exposed to a vaccuum of 1 or 2 mm. for several
hours at ordinary temperatures without releasing its gas. When.heated to
approximately 175° C. it commences to lose its gas.

Electrodeposited nickel adsorbs some water vapor, but the pre-
dominating adsorbed substance is hydrogen, prObably because of the smaller
size of the hydrogen molecules, which allow them a greater penetration than

the water molecules.

17.

Whether the presence of hydrogen has any deleterious effects
upon the nature of the nickel deposit was not ascertained. however, it
has been shown that whatever may be the ill effects of adsorbed hydrogen
they are not increased in the low pH baths where gassing is great er. Of
course greater gassing may have a tendency to produce a more honey-
combed structure even though the gas may not be adsorbed.

A very interesting argument was instigated by an article by
Harding and Smith (J.A.C.S., 40, 1508-31, 1918). In this article it was
stated that while hydrogen was being deposited upon a metal, the re-
sistance first rose to a maximum and then lowered. The rising to a maxi-
mum was explained by assuming that during this period an alley was being
formed, and the lowering was explained by assuming that a transient type
of hydrogen which was conducting was then being formed.

Newbery (J.A.C.S., 41, 1887-92, 1919) criticises the formation
of a transient hydrogen. He believes that hydrides are formed under the
great pressures produced by high current densities, and are decomposed on
cessation of the current. He bases his argument on the fact that the
single potential of platinum electrode saturated with hydrogen is some-
times .72 v. higher than that of the hydrogen electrode and, therefore, a
hydride must be assumed.

Harding and Smith (J.A.C.S., 41, 1892-4, 1919) return with more
proof of their theory, believing that on the basis of the hydride theory
it would be necessary to attribute to such a compound a volume condensation
greater than that of the metal and of a higher order than any hitherto
observed for compounds or solid solutions. on the other hand the accmrm-
lation of transient hydrogen may raise the electrical solution pressure of

hydrogen and in general involves no sweeping assumptions as the co-existence

of solid solutions and metallic compounds.

18.

Summary

This work can.not be classed more than a preliminary survey
of the adsorpiton of hydrogen'by electrodeposited nickel. The results
are considered accurate to within 0.10 cc. at standard conditions.
The amount of hydrogen adsorbed on.nickel has been determined at the
pB's 5.6, 2.8, 1.7, and at the current densities l, 3, 5, 7, 9,

amperes per square decimeter.

 

 

 

'1‘! b ' Ik
- 9 .. 1 a...
'- I‘. W,‘ a I‘: ;
.3e*.sI,
0 ~. . _‘ r . ~
I '1‘; .. (a: r” 3
.o.‘ "v."7"-,-v'~:;,5
,o ." '2 1 . .3
".I .Ir“"\' '.. :‘? ’4.
i I '. 'W.‘ 1' J43
. 0 ’ ' '\
"3)"! '9": 3-: , : 0'!"
.- .|"a.'*. .TVV‘.’
.. 3. .' {,1 6 , ‘. I .
I J ‘hfn . 4'? , 'v
o. O ‘00 "i I".-'[ .I I "é
lqt “’°.“'-'L.' "-f.'
. 0 " "‘A“ I ”:5“. ‘ .
v‘ A? ‘, ‘ . _ "‘ -'-
”o“ .E 5‘3",” ' .(I,
\ I t .3... ‘~* ‘ 3.1: t if f‘.
l f"
'V’

 

T546

0593
Clark

3;} o l-
I‘ ’J;’- "'

..-
-.":.

94650

It" {7 "I ". .
4.13.4.41’ LI

  

   

 

m:

' J.
\"'- 4. 33;... t- x 1.3
)9‘1...-A‘1w.=“_

      

  

  

. V! 1'. u
. . " P“ ‘ (h
.mtgfiwfi
- 3-: 1" Jr" " ‘3“! .
. 11 . ‘ . -.
‘; .' 3.33.. I915";
r}- '13'.:,_v'..-;..3
< \ "v. “I? Q ‘. 1
a _ .‘c . "2.!
‘ .1. army-A \ ,
'. ..!II.¢'."~' :1:
I, o ‘ ‘nr. .._ I.
' wt: . N), 1 3 - *-
3- .0 ‘al‘,’ Q ‘2 .{VI' 'I-f I ‘I ' ’-
.-' 0‘. |s\\ ’ ".'. ‘ i' ‘\",., ' 1 n a .
.:.,.‘<.. ‘. YtJ ~.‘ ‘~ ‘1
h ‘ 'c' *1 l t. 3, .""...3“($f '2‘qam‘.’
V,-.,.., ~IJM’ - ~-
‘ 1 _ O 'o 4 . (Vt. ‘u‘ l ’ -’ '
h , W.“ 9‘4? q 1&0 {Mug '\3. {1..m‘3i
. oflf ~ w“ Hid/21""- V": .4)" "“"‘:'J I 1
1 --<" ' n, Ar.v vt-V
. ' 1.». ;" .. ..'-$;rl '9‘: 3 ‘1 'r‘i"? Ifi‘l ' '3 «*3 I W
~ “7:13,. .. . ~~, ”turf... '. ,
\I ,., ‘ .3..-. ‘-. __‘/‘ 1", ‘,.'.N h! ~
"‘ If." m" .' )4. A: '_- v 1")"; 1 33.31: 9.319%; )‘3‘. :‘1
‘t we»; I..'. 1343' ‘3‘ We“: 1 19333314»; I”.
~ a. ¢.*~rweeaw~tu»
:\ . .1. ‘3‘?" .' )1“. ‘3"; -£‘.1._\\". '3'... _ ,'.'
~“"",.'Ui..I JIIIW ' ‘.‘$"'I»fflr '1 (3’3;-
3Po'..‘- ." ‘1 0": I ‘_ - ' .b.
. 9- . a . .9.
. Lo".'.{r,‘u..s .' 3‘"! V ' H "a vat. ‘1'], ‘ ft )1 ‘1"'
. s_ll ‘ .‘ -\"- ‘ 4:. $10" k201" giaifli‘gz. .' :‘w
.".‘ ';...; [r ‘1“;J. {‘35. ~ ‘~ I‘
'~“&: w~ wj- . rt Pi“-
I...r.;- ~ Lmr g I. 1o. ; . 1.3.3.. if;
. O, u . ¢_ 1 o .. U a v {'1 '4
(sh 17- . u,."’ 1L: 3-.- If???" 1". ‘
' ' "3" v 0. :.,‘. 1 \‘ " .f
' .J‘4‘l '31 . -u' .. .".3 ‘1‘?“ “:391}? I fl
1 .Y I (1: _' '. . ,-' - . .‘ . ' I. ‘, I; :3, I. _.. ’3 fl“! ‘\‘-‘_ '0‘ :r t: tr 1: ‘13 )"{v'1_" “(a . . h ‘ ‘3‘ ’1‘" L
'-O . ’1 o.-,~.‘-. ‘ 'v\ F r . 2v .3} .' ‘: 1' 3.." 'l' ' J:\-‘H‘ 'x’.‘7,«.:. ' 0" 'L't'flJ'J‘ #JV “"9." r W 4“,
.o x .1} - Ml . .t' -.~ 1": u‘ ’ 1:". 'u ’ . - . 4; ~»" ‘.""'-’.3'-‘ 1' 9 n .W - Ms" ‘u-u.
l 1 _- “.31.. wig, ,3 3‘”?! . In... ., .v,3.\ ‘2." .- - v‘!’ “'1..~‘,‘ae- 1* ,"‘" 3 g 5:? . I ‘Ir-cr: ‘- Air-:3. fi‘i‘v' pg», £6. "5 33) 3 A. ’. Lat:
' .2 b- y, 2.‘ .,..- ' ,u '_ '0' 8“,. ,, .- , .. .‘ .‘ I'.“ ‘31; 1.: ”a -. ’3'- .g,‘ .- . {31. . _ , “a,“ v .j v” 1‘ )3‘. 13A :3. '53.:
' ’ 92*“ '} l " .“l t." "."’ £_ ' .‘d‘w V."-.“ ‘-&g&‘.." ."2‘ ‘ "3T '(dfi’ 4'. ~~’.$1;II‘ f (a. .) _\ '1'!!',7("' \__‘ 5..
~. ~... 1w: m- : .4 a.“ “can! -.~:-«* . ":o.‘1:' .542: :4 v. :4 win? .I‘ 51:4: ., 7 ‘13:. "a: _...-,-, 5:“ it’
. '. 7 3'. .~ 1;" 3%.“. 3r: M3513. -. ".3 ’2 . H 1. :3. . 3‘33, 7 .3. ”3,“;- ,“.",“1’»;. If“ 1 ‘1‘“ [- )‘LA. 82:33:31? 1'. 3.332%; #333533 5‘11 .53..
.- .. s- of. . '-'h w; u’w'. ."f' ‘2.” ‘ 4... ‘-~»p..".u.* z" 1‘6. ’~..«-~‘e..-=.-~«u It ~ ‘.».' .4. t '<-'- - ‘
~. I.).‘ .‘:I 3 3.. 1“? ’4 ,I ~ _ ‘Z?"‘ .. 3?‘ 3' I)" vll“ “4";13 ‘V’I‘.I.“'.u?t“_‘ L“ q ;‘t_.‘,. I’;-?~"'. ER. .2 44533;!" t.‘ ’;‘I& ’1 '2' " a'fil‘.’.$' 1‘ firvhp. "
. ~ In , ' -. x: _ . ‘. l't‘ ,- u 3. 3 J ‘ t O ‘I‘ , I . - .‘ . ‘ ~ - -"._‘ t. .. ~. 3» , . . . f.
‘ ‘ ‘0 1.} L'T')‘ - -\ "H. ' “3‘. H "fik'nti 5",»‘F‘ Y 1’ '. ’i M L‘ :1;".‘V k~pgfi .~3'%;'v‘£1 ”ti:- 3:?" "’2 gay)“, 1‘... fi'fi' " ".N't \l'te- A? ’ is]
- ' n . 1 - ‘. '- . . ' , .. ~ . '. ’ . '- . -' M -. .. - -
u‘, .., W ~_3 '5. a, _i_~ 7" "‘5. ‘ ,. I Mfr I .l)‘}3$.r‘ , .31‘39.!#.‘_..34“l, “.113 $1}. I.. i¥"_‘-‘ f ,4_ *I ”fin ”:1. ,II :3 ‘ . it I. .59"'!!.."
‘ M 3,1,“, 3" 3* ““..\“‘v“_-' 1,":- .y# . 3 . ' ‘3 I ‘ "- "I‘f '.‘.°, .I..‘. ‘k‘.i 3' ' ."-.‘_'_'7 a: ' JI'N \a?.. '3 I da‘“:" 37... .
r -. ' .m' . ’ ‘i‘ ‘5 .~ 95. -5-- ”WP-'1 4.1,," "-1.. ‘n. L.‘ R Jr 1'” 'n'r ““3 ‘.v c ,*;J_:;-;.~'38‘- 1%” -"‘ -T~r- -'-'..-.v'<. 'c'. ‘” '9 )'.. “'3
- . r‘ 'q . f 'I ‘ ‘ 'hv “‘ ‘ "'11 . E‘ ‘Z‘ A 3 i" '1‘ ~ ‘Yz'p' f... . ' ‘ ‘j’ . I I '—'~$\' - 'Lg‘w' J; .: 'I I {.51 it. '3’" 0'; XiV‘Y'
.. v. ‘4 ' ”,3". ) I, . n . 0 .1" 3 w a, in, m . .-; 3. 'R."'.‘- ‘ _. a J, ‘3. .‘K‘t-‘E...- 1),? .‘ ‘1“r... .
. 1 —‘ ' ‘5'! ‘ ”'1". " A'v: * ~‘"".""'~' 1‘ | ' \1/3 '1’ ‘ ‘ ' sh, 1 iv" '..L.t"'.-"-’\ 3'1“.""w‘, ' "~ u.'v..“'l4“
' " (1‘ ‘L‘ 1.’ ' ‘3‘ I - f :H'." a; - ‘ f ’7 ..' . ' a. 3!, .‘ '_".n 3'" 0"}. al‘g'J-g‘. “.513 .313: ‘-' .13'" V . my". .1135», 5‘; 3 b4”:*‘“ {to
I. I‘ 33:41 ‘1; ' p; o‘fy' - i 1“.“ iii)“: L. . H.“ t ."t';"‘.. '0 '3‘, J ! 3:3 ‘1'? .4" -;.0~ L_v':’ it i. ”‘7" :3 ’r‘-'. 7) 0‘ 't“." ‘i‘tl‘".)‘.‘-‘ I“; ',
' ' ~, I .-| '0 VI .-3 “.- ‘I'J. . - -L' ' I r. ' ‘g’ . l ° .‘I
. '4 ' I v - q . '. . '. .o" . . I I ' ..' - f -y ' " 1'. . P ' u .‘ 3 , H - . ..‘ .
"u 1’“. . 1' t .15- " " 4'6 'SI' ‘fLC “ " ‘ .3 'P J' V ~‘v I f '1. ' ' "1‘. in C.“ {3" v v' ‘ . “'1 V“! 1' " “- f1 1". “ ‘fs '1 ”H 42‘
--:'J‘.,t£ry‘- T‘pw :91" 3 ‘2‘7' ‘ - ~'. 21.3.. . a“, ’ - . a" .1 \.- ' . . ,‘w'rfl-J . .33 1" "+393!" ‘ "3‘1“", .
-~".. “-"i‘r- ‘-. ., .‘A ' ‘.;'.-,- r M ‘ . .v * a ‘ _. ‘ v.1}. We}, .1 1.1. . _ ". 1:131,“ x 1." :1! 3"-
.{aua;;....h y e~2"-»a a} --““ "?”.N asv a. ‘Nfiu‘h‘~@€” +;'~W?:5fi'i1"t.yw x“-~:
L..-'.'.‘.:"1r:;"‘ '5.» .71.)? ‘-_-t".’a'3 .0 1 f, 4.x", {3... J , "5.1 ”,2; {1 ft” 1 .- "4;. «'"I ‘. "j' 1 ”a ,- RM; 5: 3.1; ,,' 3’34“; :3 3 *5: f ,'
.', '. .3,‘ I]. "A ”3‘ ’3‘. .‘ 0V! ‘ a." u‘ ’,'c. ‘7. 1‘ .' " f..‘:, “.4‘.‘ I3 . f. , ,3 'i"' -., ' fwd“. .' .“ .. c..- K.“ A; ‘5‘. O. ‘;L t ‘ ‘ |.‘ .y ..‘I ’.4
1.1,. 0‘ ‘i‘d' ,_J 4 at” I__.. ‘.'.", . .3. j, . '-.'.-'.'. '3 .1! v”. o: . .', , . r- .1, “Th, I). .3 . ‘I ’3 ‘31 3 . U .- 3' \ '6
‘ b" Lib.- ."‘:l'.‘:~ 3- ‘~."«:‘« é, _’ 5‘4 . ."2‘ "M; v ,3 ;--',f .". ”'35.. ’ .42 ' "2‘ ’4; .-.-"-3" ‘n. 3‘; 4' 03' 95*); '1‘ r-
- I _ 1- . .~‘. 9 [ A - l .l . W . v' N . 4 - . . . a . . \v , . 1
’_ ‘1'. w"? ;,.‘,._~ .w - .» -. I . , 5.1% .~ met). .13, - r, \‘I1-"I-V-.v,.." (I ,, y, "WM-U" (m3 5‘. .,..
nu : ‘. "n“ 4‘, g b"; 3.." 3“..- - i r" ,v.- V f. .",-\, -. I --"»‘ r'ufi“ ' --f_ ‘33: 'n.‘ :3 3'" ' N u .3 . :31? 1 ." "w I
. .— 13 .u' ._ .1 . '_ .‘e ',{ .’ ‘I- 7,3,. ‘ :0 . 3 . r."1 v -\ g 3" . " .I .:,~. '-.I I. . . ' ' '1..\' .-'- 31 ‘- q. r L': {Q h" .
“'Qmmwn'tfifi”fk.xtwwm-'sMW?““”W~“itwn%r.xf¢ru.W&Wx
0 - 3-, '- 1‘. 3 .L' “-‘ A“ ' '. . ‘ .. 0 ' V I ' ‘~ ' ' HT . ' ' $33 - ' I, '1 .1“ - ‘
I._ 3 1.. ‘3 . ,1»... [-1 .;- . 3 I If“. . 3..-, 3 . . - 3, 53,. 7' .. ‘0 _._~ LI.“ . . .' 1‘ )2" . , A .‘ .
"qu‘ 5?"! ';\ ,4. ”a a “ OP . ‘ ‘L‘l'i\ *"'.’:~' '“ . . ‘l . 1 3 d “.= ,l“. ‘ V’I a ‘ . ’3" , . ‘ : g." I , ".‘j .1 ‘1‘ {‘7 a .' "t": ' I" ”‘4': a. “J. ‘5. 2y "" .
4 4- ' '.-.'.-_ '1“... )‘.-°-'f~', -.'- ‘- . ' 1 ‘1». '0? ,'_. 'j." . -l- -',"'-" ,- ‘ "
'u .'£Ul. ‘. ‘1')“; “r", . .}‘fl_ “3‘ LJ‘ "(2’ 5‘ “‘- I- "w '1‘0": . ‘ - 1%.} .14 '\ r 3": ’ .‘0: .‘ I .\ $9.. “ f-“'{oéfi fi‘ ". 4“ I. I “ ‘| l. 1‘
. ' , ‘q' .- fl - ‘ . ’ I, ' . . I! . ‘ a ‘ ’ .,- "3 . _ ‘ I I , ' 3‘ 3 '2' ‘ ‘ a ' . 4 .‘
, . "3 ' , 13 '[El fu- C‘j‘ '1’”? . 3“,”: . . L "'..":.4‘ .1 _‘.. I - . '4: 3.- "'r 3" 3.1. I '2.- K; {a 3. . 3.3 W _\.J},'.', “of "A
- . - I s . -n t — 4 r- . . . .3 ' , F 5 - -1 I_ - _‘ D . ' - v
V. ‘3'»; 7' I‘ " f .‘ 1 .~ .1. 1 I. '. n-It' '. -. "-v ".1 "51"W' ~ 'I1‘133‘P'31-~i ""r w
. . . f I :- I 7" X"... " ‘1’. I I "V. 55‘ .\ .. ..' ." ".‘ . - . — '3. . ." . wk? ‘ .- I. "n ”I I. 1‘ 'r- “g ‘t "\ |l “O’Ni o .I‘I-‘O.
I 1“,". “a F‘ ‘ ’ 27' ‘A' Q t'. ‘ i ‘ J "I .F‘ .-' I ' '. v) ~' Li 'I I . 5 ‘1‘! \\,;;.£“ ‘ t 1 . ‘ . ”I“ . a) ’ 'J " "1. 3 ‘ U.
)3 '13:. ..,I . ._ 'J 3 '. w ‘ 3 i... 3 . ’1.- 3... 0-5' I ..I .‘t' h ‘ . \ . I..T . ‘
'. 4' ' ). h." ' -- 5' 0 "4 ”'IJ" ‘ I 1'—"’ h ' 3‘ V's,‘ '. .“.'£.' "L '3' -‘ ’ J 1' ' ‘
o " H- :‘I ll“ fibcfi'g' ' \‘1‘ '5 7";‘. ‘4 5 3., v a tut): 3“." "ft-'9 .14 ". ’l 1 -' . ‘
. H -‘ r 3 ‘p, T'. I" ' " o'l . ‘
‘ 3. 3 i ‘. 1‘. ‘ | .) '10 .

O

IIHIIIHIIHIlllHHHHlllllIllllillllllllllllltllHllllllllll

 

31293 02446 8260