.‘ u... THE EET-ECT or AnnmeN AGENTS 0N SURFACE SMOOTHNESS OF ELECTROLYTIC NICKEL Thesis for The Degro'o of M. S. MICHIGAN STATE COLLEGE Edsel Chap-man Lain‘g‘ 194.8 Thisistocertifgthatthe thesis entitled "The Effect of Addition Abents on Surface Smoctnness cf Electrolytic Nickel' Date "-795 presented by Edsel Chapman Laing has been accepted towards fulfillment of the requirements for M S degreein Physical Chemistry A TM; Major professor a .- ' THE EF‘ECT OF ADDITION AGENTS ON SURFACE SMOOTHNESS OF ELECTROLYTIC NICKEL EDSEL CHAPMAN LAING A THESIS Submitted to the School of Graduate Studies of Michigan State College of Agriculture and Applied Science in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE Department of Chemistry 1948 ACKNOWLEDGMENT The author wishes to thank Doctor D. T. Eving, Professor of Physical Chemistry, for his assistance and guidance throughout the course of this investiga- tion. The author is also indebted to Doctors Salton- stahl and Brown, of the Udylite Corporation, for the grant of a fellowship for this project. ***#****** *Illtttttt ****** **#t #It * 20:29:27 TABIE OF CONTENTS GENERAL INTRODUCTION............................... Table Ieeoeeeoeeeoeeesoeoeeoeeeeooeeeeoeeeeoeeeec PART I Introduction..................................... Description of Instrument........................ Table11.....00000000000....0...............I.... ProcedurQOOOOOOOOOOOOOOO0......OOOOOOOOOOOOOOOOOO Table IIICOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO0...... Tables IV & VOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOIOOOO Table VIeeeeeeeso.sooeeeeeeeeeeeeeeeeeeeeooeeooeo Tables VII & VIIIooooeeooeoeeeoeoeeeeeeooeoeeoeec Table IXoooeoeseoeoeeoeeooeeoeeceoeeeeeoeeeeeeeee DiSCUSSion 0f RGSU1tSeooeoeooeooeoeeoceoeoeeeoeee Conclusions...................................... PART II IntrOdUCtiOnoooeeoeeooeooeeeeeececeeoeooooeooeoee ExperimantaleeOOOeeeoeeeoeeeeoeeeeeoeeeeoeeeeeeoo Tables X & XIeoeooeeeceoeceeeoeeeeoeeeeoeeeeeeeee Tables XII & XIIIeeeeoooeeeoeeeeeeeeeeeeeeeeeooee Tables XIV & XVeeeeeeeeeeooeeecoooeooeoeeeeeeeeoe Tables XVI & XVII...eeeeeoeeeeooeeseeeoeoeoeeeeeo Tablea XVIII & XIXeeeoeoeeeeooeeeooeeeeooeeeeeoeo Table‘XXeeeeeceoeeeoeoeeeeeeeeeeeeeooeeoeoeoeooec Discussion of Results............................ COHCIUSiODSeeeeeeeeeeeeooeeeooeeeooeoseeoeeeeecoo PART III IntrOdUCtiOnoooeooooeooeoceoeeeoeeoeeoeooooeeeeoo Experimentaleeoeceeoeeoeeoeeeeeeeceeoeeeeeoeeoeee Table XXIeeoeoeeoeeeeeooeeeeecoeeeeoeeeeoeoeoeeee Tables XXII & XXIIIoeoeeooeooeeeeeeoocceoeeoeoeec Tables XXIV & XXVeoeoceeeooeoeeeeeeeoeeeoooceeoeo Tables XXVI & XXVIIeoeeoeeeeoeoeooeeoeeeeeooeeeso Tables XXVIII & XXIX...eeooceeeeoecooeeeooeecoco. Tables XXX & XXXIeeoeeeeoeeeeeeoeeeeooeeecoeooeoe Tables XXXII & XXXIIIeoooeeeooeeecoeoeeoooecoeeee Tables XXXIV & XXXVeooeoooeooceseoesooeeeoeeeoeee Tables XXXVI & XXXVIIoeeooeceeeeeoooooeoceeeeeoee Tables XXXVIII & XXXIXooeeeeoeeeoeeoeeecooeecoooc Tab168.XL & XLIeoeeoeeooeoeeeeeeeoooeeeeeeooeoeee Tables XIII & XIJIIoooeeeeeoeeeeeceoeeeecooooeoec Tables XLIV & XLVeoeeeoeeeceoeeeeoeeeeeoeeceeeeoe Tables XLVI & XLVIIececocoeeeeooeeeooeeeoeoooooeo Tables XINIII & XIIXooooseeeeoeeoeeoeeeeeooooeeee Tables L & LI...eeeeoeoeeooeooeeoeeeeceoeeeoeoeoo Tables LII & LIIIeeeeeeoeeeoeoeooeceeeoeoeeeeoooo (Cont'd. next page) Page 1 46 48 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 TABLE OF CONTENTS (Cont'd.) Page Tables LIV & LVeeoeeeoeeeoeceeooeeeceooeeeeeoeeee 68 Tables LVI & LVIIooeooeeeeeoeeeeeeeeoeeeeoeooeeoe 69 DISCUSSiOn Of ROSHltSeooeooeeeeoeeeeeoeeeoeeeeeee 7O CODClUSiOnseeeeeeeeeeeeeoeeoeoeeseeeeeoooeoooooec 76 Literature Citedeeeoeeeeeoeeeeeeoeoooeoeeeoeeesee 78 GENERAL INTRODUCTION Addition agents, in the broadest sense, include all substances other than the metallic salt and water which are added to a bath for any purpose whatever. Generally speaking, however, the term is used to define only those substances which have an influence on the struc- ture of the deposit, and thus substances added for the purpose of controlling conductivity and metal and hydrogen ion concentration are excluded. .Addition agents have been classified in several ways by various investigators. Blum‘z) divides these compounds into two classes, viz., colloidal and crystalloidal, but as he says, this distinction is inadequate since many crystalloidal substances cause the formation of colloids in solution. more recently in an article by W. L. Penner, G. Soderberg and E. M. Baker(12), addition agents are divided into two fairly distinct classes. Class I is repre- sented by cobalt salts, and by aryl sulfonic acids, preferably poly- sulfonic acids, and aryl sulfonamides and aryl sulfonimides. The concentration of this class of compounds is only limited by their solubility, for after an optimum.concentration, further additions cause no change in the appearance or properties of the deposit. The second class is represented by cadmium and zinc, sodium formte, aldehydes and ketones, and amino poly aryl methanes. A critical con- centration.is usually present for members of this class as an excess has detrimental effects on such properties as appearance, adhesion, and throwing power. This division of addition agents was the most logical classification encountered by the author and consequently will be utilized throughout this investigation. Several theories explaining the beneficial action of addition agents have been proposed, but regardless of the process, the ulti- mate effect is the formation of finer-grained deposits, resulting in.smoother, more lustrous surfaces. Organic addition agents have been.used extensively in nickel plating only in the last few'years as they are difficult to control and were thus considered impracti- cal by earlier investigators. The modern addition agents are still somewhat troublesome to control, but their effect in producing a nuch.smocther ductile deposit more than compensates for this dis- advantage. In this project, representative addition agents of Class I and Class II were used, as indicated later under each specific phase of the investigation, in two common commercial nickel baths, vis., watts Type and High Chloride, the constituents of which are shown in Table I. In addition, two salt constituents of the above baths were used separately as standard solutions in Part III of this in- vestigation and are designated as Chloride and Sulfate in Table I. TABLE I couPos ITCION ofirmmn BATHS . Watts Type High Chloride Chloride Sulfate Bath Bath Bath Bath sz/l 5J1 s-[l s-él Nickel sulfate, NiSo .6 H20 300 _'75 --- 3 Nickel chloride,NiC12 .6 H20 60 225 332 --- Total nickel, Ni 82 72 82 82 Boric acid, H Bo 4O 4O --- --- 3 3 It was naturally impossible to study all the effects of these addition agents and thus it was decided to investigate primarily their effect on surface smoothness. In addition, however, the author also investigated their effect on Current Density-~Potential Curves, and Cathode Efficiencies, the results of which are not only important in themselves but also can be used in conjunction with future research dealing with throwing power and similar problems. The present investigation is thus divided into three more or less distinct parts: I. Surface Smoothness, II. Current Density-Current Efficiency Relationships and, III. Current Density-Potential‘Measure- ments 0 -3- INTRODUCTION PART I: The Effects of Addition Agents on Surface Smoothness According to W. L. Penner, G. Soderberg, and E. M. Baker<12), some of the organic compounds of Class I addition agents, produce bright plates by themselves, while others may decrease grain size but produce no apparent brightness or smoothing effect. However, all of these compounds have the ability to carry a larger amount of addition agents of Class II and enhance their action. Class II compounds are seldom used by themselves in modern nickel plating as they produce either too brittle a plate or a plate of insuffi- cient smoothness and brightness. It is thought that the most bril- lant plate and those which exhibit the greatest degree of smoothing out of the plate over imperfections in the subsurface are obtained, when.a material of the first class is used in conjunction with a material of the second class which is so active as to cause brittle- ness and poor adhesion when.used alone. One cannot proceed too far in this direction, however, with Class II compounds, because the carrying ability of Class I is limited not only to Class II compounds but also organic and inorganic impurities that adversely effect the plate. Many investigators have studied the effects of various addition agents used in.modern bright nickel baths. Zinc, a member of Class II, has been an.important constituent in nickel baths for many years. It is not accurately known when zinc was first added to nickel solu- tions but c. H. Pr°ctor(13), mentioned its use in 1915, and it has been used rather extensively ever since as an addition agent for the production of smoother bright deposits. Many organic addition agents have also been investigated in the last few years. L. L. Linick(8), found that benzoyl acetic, diphenyl acetic, phenyl acetic, benzene- sulfonic, toluic and tropic acids produced no satisfactory smoothness or brightness of deposit. E. Raub and M.‘Wittum‘14), investigated certain aromatic nitrogen compounds and found that aromatic amines had no appreciable effect. Saccahrin in concentrations of 0.1 - 0.2 g./l. and methylene blue produced brilliant deposits. The same authors also made an intensive investigation of aroma- tic and heterocyclic sulfonic acids. .Alpha and beta naphthalene sul- fonic acids were very effective in smoothing over the surface irregu- larities and forming a bright deposit. In the heterocyclic field, furfural, pyridine and orthohydrozyquinoline were investigated and results indicated that the first and last were the best brighteners. Stout<16), and Springer<15), found that aromatic sulfonic derivatives were important addition agents. Young(22), mentioned the use of naphthalene trisulfonic acid, sulfonated oleo resins, and benzene or o-toluene sulfonamides as effective brighteners. Many other investi- gators such as Watts(zo), Ballay(1), Hendricks(6), and Meyer(9), have investigated addition agents in nickel baths, but as voluminous as is the literature, little has been mentioned concerning the specific "hiding" or "smoothing power" of modern.bright nickel addition agents. -5- In this phase of the investigation, therefore, the primary goal was to determine the power of certain Class I and Class II addition agents used in bright nickel plating to smooth over sur- face roughness of buffed steel and in consequence produce a brighter deposit. It is logical, of course, that the brighter a deposit the smoother it is, but it is impossible to judge relative brightness or smoothness visually. Thus, in accomplishing the purpose of this phase, use was made of a comparatively new instru- ment in the plating field, viz., "The Brush Surface Analyzer" which rapidly measures the width, spacing, and depth of surface irregu- larities from.a fraction of l microinch (.000001) to 3000 micro- inches. This instrument makes it possible to analyze surfaces accurately and rapidly and thus provides an effective means of come paring the smoothing effect of addition agents in bright nickel plating. The addition agents selected for this work were sodium o-benzoyl sulfimide and benzene sulfonamide of Class I, and zinc, in the form of zinc sulfate (ZnSO4.7H20), and allyl-chloracetate quaternary of pyridine (PQ) as representatives of Class II addition agents. DESCRIPTION CF INSTRUMENT A photograph of the model SA-2 Brush Surface Analyzer is shown on page Be. The instrument consists of three main parts: the motor driven PickéUp Arm, the Calibrating Amplifier, and the Direct Inking Oscillograph. The PickéUp Arm contains a piezo-electric crystal element which is connected through a lever system to a diamond sty- lus which rises over and falls into surface irregularities as it moves back and forth over the specimen under test. As the PickéUp Arm.moves back and forth in a ten second cycle, the vertical motion of the stylus bends the crystal. When this occurs, the crystal generates a voltage, the polarity of which depends upon the direct— ion of the stylus movement. These stylus movements are then ampli- fied and reproduced from.l to 500 cycles per second by the Calibrat- ing Amplifier. This amplification then actuates the pen.motor located in the Direct Inking Oscillograph which in turn drives the inking pen over a moving paper chart. The chart is drawn beneath the recording pen by a constant speed motor and a selective gear train, giving a choice of three speeds. These are 5 mm., 25 mm., and 125 mm. per second equivalent to approximately 0.2 inch, 1 inch, and 5 inches respectively. The slowest speed was used throughout this investigation. The resulting Profilographs as shown in.Figures 1-38 are profile pictures of the surfaces under test. Each graph shows four main parts: (1) calibration of surface before plating (2) profile of surface before plating (3) calibration of surface -7— after plating (4) profile of surface after plating. The calibra- tion is important in that it indicates whether or not the PickeUp Arm is parallel to the surface to be explored. The PickeUp Arm is considered correct if a pen oscillation (peak to peak deflection) is between 10 - 20 chart divisions when the Ann is raised 1/8 inch and then allowed to fall back on the surface. In addition, the B. L. 105 R.M.S. Meter Attachment is a useful accessory to this instru- ment as it rapidly assigns a numerical value to a surface under in- vestigation. This meter is the "average reading“ type, calibrated in terms of the "RES" value of an equivalent sine wave. It has a 0 - lO micro-inch scale, the readings on which must be multiplied by 10, when the attentuator located on the amplifier is set for 0.01 as was the case throughout these tests. The same values can be calculated mathematically from the graphs, but the meter is faster, very accurate, and may be sufficient alone if "hill and dale" chart profiles are not needed. mmw>h1 In .1 T Illa“! 1 4 . t P _ p _ b _ _ p _ ”I '1 ‘3.th M 0M”: succeed at [sustains wad-ma OM10: ..a 8.83 .n .2 I; .. 33.3 931 6.3 .8... ire-o .218.- gflfl alas-o 32.8 -23.»: a! con 1 of} I. 31 g o..- oA 0." o... - l - - - 4 - - a n. l 8 l S l o.- l 8 )1 4 > a _ _ _ _ _ _ a _ .2 822.... .o .2 3228 .- 3 .53.... .. .856 2?... Joe. 1|... .355 his... alt-0.6.83.2. ear-.30 8.58 .26: .8 .3 .3- ...II. 5 2......- 32.8 o:- o.n 3.. ed a a _ d _ _ _ L 8 l 8 l .a l 8 p L 8 a!!! i All. 1 b . .. 4 .1! l 8.. _ _ P L - - _ _ W4 H1 “tau”! m3 09001.3 'weuu I: tee-sour: ma 0mm DISCUSSION OF RESUITS PART II The data and results obtained in this phase of the investiga- tion are shown in Tables IX to XIX and graphed for further simpli- city of comparison in Figures 39 - 42 inclusive. The results at current densities above 1 ampere per sq. dm. were reproducible to within approximately : .5 percent, whereas at current densities be- low 1 ampere per sq. dm. where the slope of the curves are more vertical, the reproducibility was only within 2-3 percent. All of the solutions investigated with the exception of solu- tion 24 exhibited cathode current efficiencies within a range ex- tending from 95% at low current densities to 99.9% at high current densities. The efficiencies of solution 24, containing sodium o-benzoyl sulfimide, benzene sulfonamide, 16 g./l. of P0,, sodium lauryl sulfate and sodium.fluoborate, however, varied from approxi- mately 80% to 97% as is shown in Curve B, Figure 41. Solution 13, Curve A, Figure 41, contains the same constituents as solution 24 with the exception of the P0 and sodium fluoborate and its effi- ciency is 16% higher at the lowest current density. This differ- ence is minimized, however, with an increase in current density until at 4 amperes per sq. dm., the difference is only 1.5 percent. Thus it is readily concluded that nickel solutions containing P0 and its non-pitter counterpart sodium fluoborate should be operated at cur- rent densities in the vicinity of 4 amperes per sq. dm. for maximum efficiency. -42 - Figures 39 and 42 indicate a slight beneficial effect when .9 g./1. zinc sulfate (ZnSO4.7H20) is added to either the Watts or High Chloride baths, but this is only approximately 1% which is not particularly significant. .5 g./l. zinc sulfate (ZnSO4.7H20), however, shows no effect above 1 ampere per sq. dm. and very little beneficial effect below, which indicates the importance of concen- tration of zinc in nickel baths. In Figure 39, solution 10 containing benzene sulfonamide and solution 13 containing benzene sulfonamide plus sodium.o-benzoyl sulfimide appear to be somewhat beneficial at current densities be- low 1 ampere per sq. dm. and slightly detrimental above 1 ampere per sq. dm., the latter solution lowering the efficiencies slightly more than the former. This indicates that sodium.o-benzoyl sulfi- mide has a slight harmful effect on cathode efficiencies. No con- clusions can be advanced as to whether the two above mentioned addi- tion agents actually increase cathode efficienqy at IOW'current densities or not because the slight improvement is well within the experimental error. Figure 42, curve C, shows the same tendency for sodium.o-benzoyl sulfimide in the High Chloride bath. The curve for solution 19, Figure 40, is rather interesting as it indicates that a solution containing both zinc and benzene sul- fonamide lowers the efficiency of not only the standard bath, Solu- tion 8, but also the solutions containing either zinc (Solution 16) or benzene sulfonamide (Solution 10) individually. This would sug- gest that either is somewhat detrimental to the other but the -43- benzene sulfonamide has a more harmsul effect on the zinc than visa versa. In the High Chloride bath, as evidenced in Figure 42, Solution 34, containing both addition agents of Class I plus zinc, has a lower efficiency than solution 36, which contains only zinc as an addition agent. Here again the Class I addition agents have a harmful effect on the beneficial properties of zinc. -44- CONCLUSIONS The important conclusions gleaned from the results of Part II are: l. 2. 3. 4. 5. PQ is the only addition agent investigated that shows signifi- cant harmful effects on the cathode efficiencies, especially at current densities below 3-4 amperes per sq. dm. For maximum efficiency of solutions containing PQ, the current density should be at least 4 amperes per sq. dm. Zinc, sodium.o-benzoyl sulfimide, and benzene sulfonamide indi- vidually or in combination have little beneficial or harmful effect on either the Watts or High Chloride baths. Zinc definitely effects a slight increase in efficiency at the higher concentrations. The Class I compounds shoW'a slight detrimental effect by them- selves and also decrease the efficienqy of the solutions con- taining zinc. -45- INTRODUCTION PART III - Current Density - Potential Measurements The author found few publications dealing with the effect of addition agents, in nickel plating baths, upon current density - potential relationships. J. Haas(4), added benzoic, tartaric, acetic, and succinic acids to nickel baths and found they displaced the cathode - potential curve too far to the negative side to be of value as addition agents. Haring(5), found that sodium citrate and dextrin increased the cathodic curve negatively in nickel solutions. He also found that an all chloride bath caused a more negative cathodic potential curve than did a pure nickel sulfate bath. C. T. Thomas and W. Blum‘17), studied the anode potential - current den- sity curves for various nickel anodes in nickel solutions. They found that abnormally high anode potentials were present in nickel solutions free of chlorides. This is attributed to anode passivity. The same authors also mentioned the fact that a high anode poten- tial is directly related to the resistance of the bath. A few tenths of a volt difference in potential for any given current density is insignificant, but a difference of over one volt may cause the power loss due to passivity to become appreciable. Dorrance and Gardiner(3), also noted that the chloride ion causes a large shift of the anode current density - potential curves to a less positive value, thus indicating the corrosive ability of this ion. E. Raub and M. Wittum‘14), found in studying nitrogen compound addition agents that formamide, urea, and urethane increase the cathode potential curve negatively. -46- Sulfur compounds such as thiourea also displaced the curve toward the negative side. Protein addition agents such as dextrose and sucrose displace the curve to the more positive side. The weak brighteners of the aliphatic class appear to have little effect on the curves, while the strong brighteners cause an increase in the cathode curves toward the negative side. W} A. Wesley and E. J. Roeh1(21?, also made some cathode potential - current den- sity measurements using four modern nickel baths, but their inves- tigation was not concerned with addition agents. Since comparatively little research has been conducted in regards to the effect of modern addition agents in potential curves, it was decided in this phase of the investigation to obtain anode, cell, and cathode potential data for several of the solutions in Table II. The current density-potential curves thus obtained can be used by themselves or in conjunction.with other information to explain many phenomena of nickel deposition such as throwing power, anode corrosion, and structure of the deposit. These problems, however, are beyond the scope of this investigation for it is merely the intention of the author to secure useful curves that will indi- cate the effect, if any, of addition agents on potential measurements. -47- EXPERIMENTAL All measurements of cell, anode, and cathode potentials were made in a four compartment pyrex cell, each compartment being 5 inches deep, and 1% inches in internal diameter. The first and second, and the third and fourth compartments were connected by ground-glass stopcocks, whereas the second and third compartments were fastened together through a glass connection 3E.— inch in inter- nal diameter. The cathode was of sheet steel coated with nickel deposited from the solution.under test and having an effective area - of 1/120 sq; ft. The anode was electrolytic nickel having an area of L/lSO sq, ft. The electrolytic temperature was maintained throughout most of the work at 50°C. by means of a constant - tem- perature water bath. Some determinations were also carried out at 25°C. and 75°C., for the purpose of comparison. A Leeds and Northrup Potentiometer, and a model 280, Heston, d.c. ammeter, each scale division reading .002 amperes, were used to measure voltage and amperage respectively. The anode and cathode poten- tials were measured by means of separate 1 n.calomel cells placed in the first and fourth compartments. The composition of the solu- tions used are shown in Table II, and were prepared exactly as ex- plained in Part I. During a run, the solution was placed in the cell to a depth of four inches or just above the stopcock connections. The ground glass stopcocks permitted the passage of current but at the same -43- time prevented any diffusion of electrolytes. The cell was then placed in the water bath and allowed to reach thermal equilibrium at 50°C. The calomel cells were then placed in compartments one and four. The anode and cathode were then placed in the center of compartments 2 and 3 respectively, directly opposite the central glass connection, and fastened securely 2% inches apart by pure nickel wire suspended through rubber stoppers. The electrodes and calomel cells were then connected by means of copper wire through a threeway switch to the potentiometer. An external circuit con- taining a 6 volt storage battery, a 3,360 ohm slide resistor and the ammeter was connected in series with the cell under test. By means of the slide wire resistor, the current was gradually in- creased in the external circuit, and by a manipulation of the switch, the anode, cell, and cathode potentials were obtained directly for each current density. The current was permitted to reach equilibrium, which it usually did, in one or two minutes, before taking any poten- tial readings. Since relative effects only were to be determined, and since the resistance of any one bath would be constant, it was deemed neither necessany nor important to measure the IR drop of the solution. Throughout these measurements the calomel cells were connected to the positive and the two electrodes to the negative poles of the potentiometer when anode and cathode potentials were desired. In Tables XI - LXVII,the potential values are shown in reference to both the calomel and hydrogen electrodes. The latter values were calculated by subtracting all measured potentials ~49- from +.2800. Either values would be perfectly acceptable to use for comparison of results, but the hydrogen scale data was used in the plotting of all anode and cathode potential curves. -50.. All potential measurements recorded in the following tables (XXI- VIII) are expressed in volts. The anode and cathode potential measurements as obtained by means of the ln.calomel cells are con- verted to the hydrogen cell scale by subtracting all values from -.2800. The cathode area equals 1/120 sq. ft. and the anode area : 1/130 sq. ft. TABLE XXI CELL,.ANODE, AND CATHODE POTENTIAL DATA Temperature - 25°C. pH : 3.0 (electrometric) Amperes Cell Cathode-Potential Anode-Potential Potential Hydrogen CalomeI' Hydrogen Calbmel .0001 .3440 -.2750 .5555 4.0130 .2670 .0005 .3680 -.2950 .5750 0.0150 .2650 .001 .4032 -.3300 .6100 +.0315 .2485 .002 .4650 -.3600 .6400 +.0465 .2335 .003 .5180 -.3750 .6550 4.0649 .2151 .004 .5660 -.4070 .6870 +.0800 .2000 .005 .6155 -.4165 .6965 +.0930 .1870 .006 .6535 -54230 .7030 {.1058 .1742 .008 .7145 -.4350 .7150 {.1188 .1612 .01 .7750 -.4460 .7260 {.1270 .1530 .016 .9290 -.4625 .7425 4.1395 .1405 .02 1.1300 -.4740 .7540 +.1510 .1290 .03 1.2760 -.5018 .7818 4.1570 .1230 TABIE XXII Solution No. 1 CELL,.ANODE, AND CATHODE POTENTIAL DATA Temperature 2 50°C. pH : 3.0 (electrometric) Amperes Cell Cathode-Potential? Anode-Potential Potential Hydrogen Cdlbmel' Hydrogen CaIOmeI .0001 .1765 -.2880 .5680 -.1200 .4000 .0005 .1925 -.2890 .5690 -.1075 .3875 .001 .2095 -.2890 .5690 -.1000 .3800 .002 .2445 -.2940 .5740 -.0820 .3620 .004 .3060 -.3025 .5825 -.0550 .3350 .006 .3470 -.3090 .5890 -.0505 .3305 .008 .3885 -.3180 .5980 -.O385 .3185 .01 .4335 -.3250 .6050 -.0300 .3100 .02 .6255 -.3495 .6295 +.0095 .2705 .04 .9575 -.3785 .6585 +.0515 .2285 .06 1.2700 -.3970 .6770 +.0755 .2045 'TABLE XXIII Solution No. 1 CELL, ANODE, AND CATHODE POTENTIAL DATA Temperature 2 75°C. pH 2 3.0 (electrometric) Amperes C611 Cathode-Potential Anode-Potgntial Potential Hydrogen Calomelfi‘ Hydrogen CalomeI .0001 .1155. -.2530 .5330 -.1440 .4240 .0005 .1185 -.2540 .5340 -.1425 .4225 .001 .1305 -.2545 .5345 -.1350 .4150 .002 .1530 -.2575 .5375 -.1270 .4070 .004 .1920 -.2625 .5425 -.1130 .3930 .006 .2220 -.2650 .5450 -.1070 .3870 .008 .2490 -.2675 .5475 -.1000 .3800 .01 .2740 -.2715 .5515 -.0980 .3780 .016 .3470 -.2765 .5565 -.0840 .3640 .02 .3940 -.2815 .5615 -.0830 .3630 .03 .5020 -.2860 .5660 -.0685 .3485 .04 .6050 -.2920 .5720 -.0650 .3450 .06 .8440 -.3015 .5815 -.O450 .3250 .08 1.065 -.3090 .5890 -.0365 .3165 -52- TABLE XXIV Solutian Ho. 2 CELL, ANODE, AND CATHODE POTENTIAL DATA Temperature 2 50°C. pH 2 3.0 (electrometric) Amperes Cell Cathode—Potential Anode-Potentidl Potential Hydrogen Calomel Hydrogen calomel .0001 .2145 -.3005 .5805 -.0890 .3690 .001 .2600 -.3165 .5965 -.0805 .3605 .002 .3145 -.3340 .6140 -.0610 .3410 .004 .3988 -.3625 .6425 -.0480 .3280 .006 .4505 -.3690 .6490 -.0300 .3100 .008 .4835 -.3725 .6535 -.0265 .3065 .01 .5220 -.0190 .2990 .016 .6415 -.3810 .6610 -.0100 .2900 .02 .7220 -.3850 .6650 -.0000 .2800 .03 .9155 -.3810 .6590 4.0200 .2600 .04 1.0910 -.3800 .6600 9.0360 .2440 TABIE XXV SOEIOH NO. 3 CEIlu ANODE, AND CATHODE POTENTIAL DATA Temperature : 50°C. pH = 3.0 (electrometric) Amperes Cell Cathode-Potential Anode-Potential Potential Hydrogen Calomel Hydrogen Calomgl .0001 .1750 -.2850 .5650 -.1220 .4020 .0005 .1900 -.2880 .5680 -.1090 .3890 .001 .2075 -.2900 .5700 -.1000 .3800 .002 .2410 -.2920 .5720 -.0825 .3625 .004 .3025 -.3000 .5800 -.0520' .3320 .006 .3450 -.3070 .5870 -.O5OO .3300 .008 .3865 -.3150 .5950 -.0390 .3190 .01 .4325 -.3245 .6045 -.O310 .3110 .02 .6240 -.3500 .6300 4.0080 .2720 .04 .9550 -.3795 .6595 +.0510 .2290 .06 1.2690 '-.3950 .6750 +.0735 .2065 -53.. TABLE XXVI Solution No. 4 CELL, ANODE, AND CATHODE POTENTIAL DATA Temperature : 50°C. pH 2 3.0 (electrometric) _Amperes Cell Cathode-Potential Anode-Potential Potential Hydrogen Calomel _ Hydrogen Calomgl .0001 .1572 -.2610 .5410 -.1155 .3955 .001 .2115 -.2830 .5630 -.1020 .3820 .002 .2635 -.3120 .5920 -.0815 .3615 .004 .3430 -.3240 .6040 -.0580 .3380 .006 .4155 -.3505 .6305 -.0372 .3172 .008 .4700 -.3610 .6410 -.0255 .3055 .01 .5210 -.3660 .6460 -.0130 .2930 .016 .6625 -.3825 .6625 0.0130 .2670 .02 .7445 -.3880 .6680 4.0240 .2560 .03 .9355 -.3990 .6790 4.0445 .2365 .04 1.1250 -.4085 .6885 4.0545 .2255 TABLE XXVII Solution No. L: U CELL, ANODE, AND CATHODE POTENTIAL DATA Temperature : 25°C. pH 2 3.0 (electrometric) Amperes Cell Cathode-Potential Anode-Potential Potential Hydrogen Galomgl' Hydrogen Calomél .0001 .4695 -.3635 .6435 +.0935 .1865 .0005 .5575 -.3915 .6715 +.1250 .1550 .001 .6300 -.4300 .7100 +.1395 .1405 .002 .7220 -.4570 .7370 +.1610 .1190 .004 .8815 -.5000 .7800 +.1800 .1000 .006 1.0120 -.5190 .7990 4.2015 .0785 -54.. TABLE XXVIII Temperature : 50°C. Solution No.v5l CELL,.ANODE, AND CATHODE POTENTIAL DATA pH 2 3.0 (electrometric) Amperes Cell Cathode-Potential’ Anode-Potential Potential Hydrogen Calomel Hydrogen CalOmel .0001 .2310 -.3186 .5986 -.0960 .3760 .0005 .2890 -.3385 .6185 -.0755 .3555 .001 .3750 -.3595 .6395 -.0320 .3120 .002 .4730 -.3850 .6650 +.0180 .2620 .004 .6160 -.4185 .6985 +.0560 .2240 .006 .7210 -.4360 .7160 +.0930 .1870 .008 .8009 -.4425 .7225 +.1050 .1750 .01 .8990 -.4530 .7330 4.1648 .1152 .02 1.2810 -.4750 .7550 4.1700 .1100 TABLE XXIX Solution No. 5 CEng ANODE, AND CATHODE POTENTIAL DATA Temperature 3 75 C. pH 2 3.0 (electrometric) Amperes cell Cathode-Potential Anode-Potential Potential Hydrogen Calomel' Hydrogen Calomgl .0001 .1995 -.3115 .5915 -.1235 .4035 .0005 .2250 -.3243 .6043 -.1195 .3995 .001 .2580 -.3345 .6145 -.1065 .3865 .002 .3550 -.3550 .6350 -.0480 .3280 .004 .4500 -.3650 .6450 -.0205 .3005 .006 .5250 -.3725 .6525 1.0045 .2755 .008 .6005 -.3785 .6585 t.0260 .2540 .01 .6860 -.3890 .6690 +.0510 .2290 .02 "" -04250 e 7050 +0 1100 -55- TABLE XXX Temperature : 50°C. Solution No. 6 CELL, ANODE, AND CATHODE POTENTIAL DATA pH = 3.0 (electrometric) Amperes Cell Cathode-Potential Anode-Potential Potential Hydrogen Calomél' Hydrogen Calomél .0001 .4265 -.2875 .5675 +.1165 .1635 .001 .5112 -.3105 .5905 +.1455 .1345 .002 .5845 -.3345 .6145 4.1645 .1155 .004 .7200 -.3635 .6435 +.1795 .1005 .006 .8300 -.3980 .6780 +.1875 .0925 .008 .9360 -.4185 .6985 +.1975 .0825 001 100350 -04595 .7195 +01985 .0815 0016 1.3055 '04640 .7440 +02118 00682 .02 1.4680 -.4775 .7575 +.2l45 .0655 TABLE XXXI ‘5‘ Solution No. 7 Temperature : 25°C. CELL,.ANODE, AND CATHODE POTENTIAL DATA pH = 3.0 (electrometric) Amperes Cell Cathode-Potential Anode-Potential Potential Hydrogen Calomell Hydrogen Calomel .0001 .3335 -.3200 .6000 +.014O .2660 .0005 .4450 -.3650 .6450 +.044O .2360 .001 .5365 -.4000 .6800 4.0650 .2150 .002 .6300 -.4110 .6910 +.084O .1960 .003 .7085 -.4170 .6970 4.1080 .1720 .004 .7730 -.4410 .7210 +.1125 .1675 .006 .8940 -.4600 .7400 +.ll95 .1605 .008 .9940 -.4750 .7550 +.1290 .1510 .01 1.1090 -.4850 .7650 +.1383 .1417 .016 ---- -.5100 .7900 --- ---- .02 ---- -.5200 .8000 --- --- 003 --" -05450 08250 ---- C--- -55- TABLE XXXII solution No. 7 CELL, AHODE, AND CATHODE POTENTIAL DATA Temperature = 50°C. pH 2 3.0 (electrometric)_ Amperes Cell Cathode-Potential“ Anode-Potential Potential Hydrogen Calomgl Hydrogen Calomel .0001 .2650 -.3160 .5960 -.0565 .3365 .0005 .3240 -.3258 .6058 -.0325 .3125 .001 .4040 -.3805 .6605 -.0160 .2960 .002 .4655 ---- ---- {.0035 .2765 .003 .5100 -.3835 .6635 4.0195 .2605 .004 .5615 -.3966 .6760 4.0270 .2530 .006 .6495 -.4100 .6900 $.0450 .2350 .008 .7260 -.4208 .7008 +.0465 .2335 .01 .8090 -.4270 .7070 +.0560 .2240 .016 1.0160 -.4430 .7230 +.0670 .2130 .02 1.1380 -.4455 .7255 +.0750 .2050 .03 1.4240 -.4460 .7360 +.0718 .2082 TABLE XXXIII Solution No. 7 CELIA ANODE, AND CATHODE POTENTIAL DATA Temperature = 75°C. pH i 3.0 (electrometric) Amperes Cell Cathode-Pdtentialli Anode-Potential Potential Hydrogen Calomgd' Hydrogen Calomgl .0001 .2130 -.30307 .5830 -.0950 .3750 .0005 .2515 -.3180 .5980 -.0860 .3660 .001 .2785 -.3230 .6030 -.0750 .3550 .002 .3210 -.3350 .6150 -.0675 .3475 .003 .3490 -.3300 .6100 -.0550 .3350 .004 .3795 -.3345 .6145 -.0540 .3340 .006 .4455 -.3450 .6250 -.0440 .3240 .008 .5065 -.3545 .6345 -.0415 .3215 .01 .5725 -.3650 .6450 -.0310 .3110 .016 .7440 -.3820 .6620 -.0220 .3020 .02 .8630 -.3970 .6770 -.0160 .2960 .03 1.1270 -.4075 .6875 e.0065 .2865 .04 1.3870 -,4200 .7000 +.009o .2710 A -57- TABLE.XXXIV Temperature : 500 C. Solution.No. 9 CELL,.ANODE,.AND CATHODE POTENTIAL.DATA pH : 3.0 (electrometric) Amperes Cell Cathode—Potential Anode-Pctential Potential Hydrogen Calomel” Hydrogen Calomel .0001 .3825 -.3315 .6115 +.0335 .2465 .001 .4455 -.3530 .6330 4.0570 .2230 .002 .5110 -.3740 .6540 4.0610 .2190 .004 .6270 -.4025 .6825 +.0800 .2000 .006 .6172 -.4200 .7000 +.0870 .1930 .008 .7940 -.4350 .7150 +.0965 .1835 .01 .8765 -.4510 .7310 +.1000 .1800 .016 1.0775 -.4590 .7390 +.1105 .1695 .02 1.1975 -.4645 .7445 +.ll30 .1670 .03 1.5150 -.4690 .7490 +.1190 .1610 TABLE XXXV Temperature 3 75°C. Solution No. 9 CELL, ANODE, AND CATHODE POTENTIAL DATA pH 2 3.0 (electrometric) Amperes Cell’ Cathode-Potential Anode-Potential Potential Hydrogen Caldmel Hydrogen Calomgl .0001 .2505 -.2680 .5480 -.0585 .3385 .001 .2935 -.3025 .5825 -.0460 .3260 .002 .3470 -.3155 .5955 -.0308 .3108 .004 .4370 -.3355 .6155 -.0200 .3000 .006 .5080 -.3518 .6318 -.0090 .2890 .008 .5860 -.3710 .6510 -.0035 .2835 001 06525 -e3885 .6685 +00070 02730 .016 .8455 -.4085 .6885 +.0215 .2585 .02 .9460 -.4110 .6910 +.O3l5 .2485 .03 1.2180 -.4115 .6915 +.0465 .2335 -53- TABLE XXXVI Solution No. 11 CELL, ANODE,.AND CATHODE POTENTIAL DATA Temperature = 50°C. pH 3 3.0 (electrometric) Amperes Cell Cathode-Potential Anode-Potential Potential Hydrogen Calomel Hydrogen Calomél .0001 .2465 -.2700 .5500 -.0510 .3310 .001 .3265 -.2912 .5712 -.0250 .3050 .002 .4220 -.3230 .6030 -.0040 .2840 .004 .5600 -.3325 .6325 +.0180 .2620 .006 .6792 -.3630 .6630 +.0385 .2415 .008 .7830 -.3825 .6825 +.0400 .2400 .01 .8718 -.3822 .6822 +.0495 .2305 .016 1.1275 -.4020 .7020 +.0570 .2230 .02 1.2880 -.4120 .7120 +.0630 .2170 .026 1.4980 -.4l60 .7160 +.O708 .2092 TABLE XXXVII Sdlution No. 12 ‘ CELL,.ANODE, AND CATHODE POTENTIAL DATA Temperature = 50°C. pH : 3.0 (electrometric) Amperes Cell Cathode-Potentfdl ‘IAnode-Potential Potential Hydrogen Calomél Hydrogen Calomél .0001 .3000 -.2815 .5615 -.0200 .3000 .001 .4060 -.3330 .6130 +.0225 .2575 .002 .4775 -.3565 .6365 +.0435 .2365 .004 .6020 -.3850 .6650 +.0675 .2125 .006 .7060 -.4200 .7000 +.0700 .2100 .008 .7825 -.4330 .7130 +.0815 .1985 .01 .8615 —.4330 .7130 9.0885 .1915 .02 1.2310 -.4650 .7450 +.1200 .1600 .03 1.5600 -.4805 .7605 +.1280 .1520 -59- TABLE XXXVIII solution Ho. l2 CELL, APODE, AND CATHODE POTENTIAL DATA Temperature 2 75°C. pH = 3.0 (electrometric) Amperes Cell Cathode-Potential Anode-Potential Potential Hydrogen Calomgl' Hydrogen Calomel .0001 .2180 -.2775 .5575 -.0710 .3510 .001 .2880 -.3125 .5925 -.O470 .3270 0002 03380 ”.3200 06000 '00440 .3240 .004 .4165 -.3440 .6240 -.0280 .3080 .006 .5050 -.3595 .6395 -.0260 .3060 .008 .5750 -.3775 .6575 -.0125 .2925 .01 .6430 -.3890 .6690 -.0085 .2885 002 09385 "04060 06860 f00185 02615 TABLE XXXIX solution No. 14 CELL, ANODE, ND CATHODE POTENTIAL DATA Temperature 2 50° C. pH 2 3.0 (electrometric) Amperes Cell' Cathode-Potential Anode-Potefitial Potential Hydrogen Calomel Hydrogen Calomel .0001 .3025 -.3070 .5870 -.0180 .2980 .001 .4165 -.3665 .6465 -.0065 .2865 .002 .4890 -.3990 .6790 +.0183 .2617 .004 .5865 -.4235 .7035 +.0255 .2545 .006 .6550 -.4265 .7065 +.0345 .2455 .008 .7410 -.4350 .7150 4.0400 .2400 .01 .8030 -.4400 .7200 4.0440 .2360 .016 1.0180 -.4440 .7240 +.0605 .2195 .02 1.1410 -.4495 .7295 +.0625 .2175 .03 1.4510 -.4510 .7310 +.0785 .2015 -50- TABLE XL Solution‘15 CELL, ANODE, AND CATHODE POTENTIAL DATA Temperature I 50°C. pH - 3.0 (electrometricl_ Amperes Cell Cathode-Potential Anode-Potential Potential Hydrogen Cdldmél Hydrogen Calomgl .0001 .2410 -.2690 .5490 -.0475 .3275 .001 .3550 -.3415 .6215 -.0227 .3027 .002 .4400 -.3720 .6520 -.0055 .2855 .004 .5500 -.3980 .6780 +.0150 .2650 .006 .6382 -.4160 .6960 4.0255 .2545 .008 .7180 -.4250 .7050 +.O380 .2420 .01 .7930 -.4325 .7125 4.0340 .2460 .016 1.0080 -.4495 .7295 +.0605 .2195 .02 1.1330 -.4550 .7350 4.0605 .2195 .03 1.4695 -.4670 .7470 4.0760 .2040 TABLE XLI Solution No. l6 CELL,.ANODE, AND CATHODE POTENTIAL DATA Temperature 2 50°C. pH 3 3.0 (electrometric) Amperes Céll Cathode-Potential Anode—Potential Potential . Hydrogen Calomgl' Hydrogen Caldmgl .0001 .2290 -.2568 .5368 -.0425 .3225 .001 .3130 -.3135 .5935 -.0240 .3040 .002 .4235 -.3630 .6430 -.0110 .2910 .004 .5420 -.3930 .6730 4.0120 .2680 .006 .6310 -.4l65 .6965 4.0210 .2590 .008 .7112 -.4265 .7065 4.0335 .2465 .01 .7930 -.4365 .7165 4.0390 .2410 .016 1.0020 -.4500 .7300 4.0565 .2235 .02 1.1265 -.4615 .7415 4.0560 .2240 .03 1.4435 -.4650 .7450 4.0705 .2095 -51- TABLEZXLII Solution No. 17 ELL, ANODE, AND CATHODE POTENTIAIaDATA Temperature : 500 C. pH = 3.0 (electrometric) Amperes Céll Cathode-Potential Anode-Potentialgfl— Potential Hydrogen Calomel Hydrogen Calomel .0001 .2860 -.3l30 .5930 -.0500 .3300 .001 .3425 -.3250 .6050 -.0260 .3060 .002 .4135 -.3510 .6310 -.0145 .2945 .004 .5225 -.3755 .6555 4.0110 .2690 .006 .5930 -.3925 .6725 4.0180 .2620 .008 .6625 -.3925 .6725 +.0265 .2535 .01 .7280 -.3995 .6795 4.0295 .2505 .016 .9340 -.4045 .6845 +.0475 .2325 .02 1.0600 -.4150 .6950 +.O570 .2230 .03 1.3830 -.4225 .7025 4.0740 .2060 TABLE XLIII Solution No. 18 . CELL,.ANODE, AND CATHODE POTENTIAL DATA Temperature = 50° C. pH : 3.0 (electrometric) —Amperes Cell Cathede-Potential Anode-Potential Potential Hydrogen Calomel Hydrogen Calomel .0001 .3210 -.3315 .6115 -.0300 .3100 .001 .3825 -.3560 .6360‘ -.0075 .2875 .002 .4445 -.3705 .6505 4.0055 .2745 .004 .5312 -.3810 .6610 4.0225 .2575 .006 .6100 -.3945 .6745 4.0275 .2525 .008 .6880 -.4030 .6830 4.0375 .2425 .01 .7455 -.4092 .6892 4.0390 .2410 .016 .9635 -.4210 .7010 4.0575 .2225 .02 1.0920 -.4285 .7085 4.0575 .2225 .03 1.4215 -.4450 .7250 4.0780 .2020 -52- TABLEIXLIV Solution No. 19 CELL, ANODE, AND CATHODE POTENTIAL DATA Temperature 2 509 C. pH ' 3.0 (electrometric) Amperes Cell Cathode-Potential Anode-Potential Potential Hydrogen Calomel' Hydrogen Calomgl .0001 .2745 -.3115 .5915 -.0510 .3310 .001 .3540 -.3465 .6265 -.O300 .3100 .002 .4315 -.3738 .6538 -.0105 .2905 .004 .5195 -.3810 .6610 4.0088 .2712 .006 .6015 -.3930 .6730 4.0190 .2610 .008 .6830 -.4050 .6850 4.0265 .2535 .01 .7565 -.4090 .6890 4.0380 .2420 .016 .9765 -.4280 .7080 4.0510 .2290 .02 1.1120 -.4325 .7125 4.0625 .2175 .03 1.4515 -.4530 .7330 4.0780 .2020 TABLE XLV Solution No. 20 CELL, ANODE, AND CATHODE POTENTIAL DATA Temperature = 50° 6. pH = 3.0 (electrometric) Amperes Cell' Cathode-Potential’ Anode-Potential Potential Hydfogen calomel' Hydrogen Calomél 00001 .2170 -e2355 05155 '00532 .3132 .0006 .2942 -.2655 .5455 -.0125 .2925 .0016 .4070 -.3390 .6190 +.0090 .2710 .0028 .5692 -.4022 .6822 4.0285 .2515 .0054 .7175 -.4460 .7260 4.0525 .2275 .0078 .8226 -.4590 .7390 +.0605 .2195 .0090 .8850 -.4600 .7400 4.0685 .2115 .0130 1.0640 -.4785 .7585 4.0770 .2030 .0190 1.3165 -.4875 .7675 4.0930 .1870 .0246 1.5585 -.4950 .7750 4.1055 .1745 -53- TABLE.XLVI Solution No. 23 CELL, ANODE, AND CATHODE POTENTIAL DATA Temperature 2 50° 0. pH = 3.0 (electrometric) Amperes Cell Cathode-Potential Anode-Potential Potential Hydrogen CalomeI’ Hydrogen Calomel .0001 .3250 -.3055 .5855 +.0050 .2750 .0006 .3625 -.3155 .5955 +.0290 .2610 .001 .4082 -.3345 .6145 +.0330 .2470 .002 .4965 -.3572 .6372 +.0445 .2355 .0038 .6065 -.3990 .6790 +.0635 .2165 .0059 .7400 -.4266 .7066 +.O784 .2016 .0078 .8360 -.4568 .7368 +.0850 .1950 .0095 .9318 -.4710 .7510 +.0874 .1926 .0121 1.0690 -.4920 .7720 +.1010 .1790 .0160 1.2430 -.5110 .7910 4.1115 .1685 .0235 1.5466 -.5190 .7990 +.1295 .1505 .0298 ---- -.5240 .8040 4.1370 .1430 .0373 ---- -.5310 .8110 +.1445 .1355 TABLE XLVII Solution No. 26’ CELL, ANODE, AND CATHODE POTENTIAL DATA Temperature 2 250 C. pH = 3.0 (electrometric) ifihperes 0611 Cathode-Potential .Anode-PotentiaI Potential Hydrogen CaloméI' Hydrogen CaloméI .0001 .3130 -.2950 .5750 +.0650 .2150 .0005 .3885 -.3405 .6205 +.0680 .2120 .001 .4340 -.3615 .6415 +.O77O .2030 .002 .5090 -.3888 .6688 +.0870 .1930 .003 .5695 -.4025 .6825 +.1005 .1795 .004 .6095 -.4130 .6930 4.1060 .1740 .006 .6875 -.4250 .7050 +.1170 .1630 .008 .7545 -.4360 .7160 +.1195 .1605 .01 .8195 -.4410 .7210 +.1235 .1565 .016 .9935 -.4565 .7365 +.1310 .1490 .02 1.1085 -.4620 .7420 +.1375 .1425 .03 1.3755 -.4750 .7550 4.1445 .1365 -54- TABLE XLVIII Solution No. 26 CELL, ANODE, AND CATHODE POTENTIAL DATA Temperature : 50° 0. pH : 3.0 (electrometric) Amperes Cell’ Cathode-Potential Anode-Potential4_ Potential Hydrogen Calomel' Hydrogen CalOmel .0001 .2160 -.3150 .5950 -.0995 .3795 .0005 .2670 -.3390 .6190 -.0865 .3665 .001 .2965 -.3450 .6250 -.0700 .3500 .002 .3330 -.3600 .6400 -.0580 .3380 .004 .3720 -.3615 .6415 -.O425 .3225 .006 .4040 -.3695 .6495 -.0405 .3205 .008 .4625 -.3825 .6625 -.0230 .3030 .01 .5230 -.3745 .6545 -.0230 .3030 .016 .6500 -.3890 .6690 -.0050 .2850 .02 .7275 -.3905 .6705- +.0065 .2735 .03 .9035 -.3950 .6750 +.0175 .2625 .04 1.0880 -.4080 .6880 +.O360 .2440 TABIE XIIX Solution No. 26 ELL, ANODE, AND CATHODE POTENTIAL DATA Temperature : 75° C. pH = 3.0 (electrometric) llmperes Cell Cathode-Potential Anode-Potential Potential Hydrogen Calomel’ Hydrogen Calomel .0001 .0970 -.2480 .5280 -.1540 .4340 .0005 .1205 -.2570 .5320 -.1485 .4285 .001 .1435 -.2675 .5475 -.1390 .4190 0002 .1750 '02770 .5570 "o 1315 .4115 .003 .1950 -.2770 .5570 -.1225 .4025 .004 .2120 -.2795 .5595 -.1225 .4025 .006 .2580 -.2895 .5695 -.1107 .3907 0008 02995 ".2975 05775 ---- --'- .01 .3370 -.3060 .5860 -.1020 .3820 .016 .4385 -.3200 .6000 -.0905 .3705 .02 .5010 -.3260 .6060 -.0855 .3655 .03 .6495 -.3405 .6205 -.0750 .3550 .04 .7910 -.3520 .6320 -.0710 .3510 .06 1.099 -.3675 .6475 -.0505 .3305 -65... TABLE L Solution No. 28 CELL6 ANODE, AND CATHODE POTENTIAL DATA Temperature : 50 C. pH = 3.0 (electrometriclg Amperes Cell Cathode-Potential Anode—Potential Potential Hydrogen Calomel Hydrogen Calomel .0001 .2390 -.3232 .6032 -.0920 .3720 .001 .2835 -.3290 .6090 -.0700 .3500 .002 .3285 -.3345 .6145 -.0525 .3325 .004 .4200 -.3550 .6350 -.O315 .3115 .006 .4855 -.3680 .6480 -.0145 .2945 .008 .5450 -.3815 .6615 -.0110 .2910 .01 .5960 -.3850 .6650 -.0040 .2840 .016 .7575 -.4060 .6860 4.0120 .2680 .02 .8575 -.4120 .6920 4.0260 .2540 .03 1.1000 -.4265 .7065 4.0435 .2365 .04 1.3320 -.4320 .7120 4.0570 .2230 TABLE LI Solutibn Ho: 30 CELL, ANODE, AND CATHODE POTENTIAL DATA Temperature : 25° 0. pH : 3.0 (electrometric) Amperes Cell Cathode-Potential AnodeePBtential Potential Hydrogen Calomel’ Hydrogen Calomel .0001 .3090 -.2995 .5795 4.0065 .2735 .001 .4295 -.3525 .6325 4.0286 .2514 .002 .5175 -.3950 .6750 4.0635 .2165 .004 .6125 -.4200 .7000 4.0900 .1900 .006 .6800 -.4200 .7000 4.1075 .1725 .008 .7400 -.4180 .6980 4.1165 .1635 .01 .8130 -.4350 .7150 4.1238 .1562 .016 1.0010 -.4475 .7275 4.1415 .1385 .02 1.1210 -.4570 .7370 4.1425 .1375 .04 1.3960 -.4775 .7575 4.1565 .1235 TABLE LII sojution No. 30 CTLL, ANODE, AND CATHODE POTENTIAL DATA Temperaturgh= 500 0. pH : 3.0 (electrometric) Amperes Cell CathodeéPotential Anode-Potential Potential Hydrogen Calomgl Hydrogen;_ CElomEl .0001 .1790 -.2635 .5435 -.1000 .3800 .001 .2405 -.3009 .5809 -.0800 .3600 .002 .2730 -.3090 .5890 -.0720 .3520 .004 .3460 -.3240 .6040 -.0500 .3300 .006 .4050 -.3380 .6180 -.0425 .3225 .008 .4530 -.3465 .6265 -.0345 .3145 .01 .5050 -.3530 .6330 -.0275 .3075 .016 .6425 -.3665 .6465 -.0075 .2875 .02 .7330 -.3780 .6580 4.0010 .2790 .04 1.1475 -.4005 .6805 4.0525 .2275 TABLE 1111 Solution No. 31 CELLé‘ANODE, AND CATHCDS POTENTIAL DATA Temperature 3 25 C. pH 2 3.0 (electrometric) Amperes cell CatBode-Potential’ Anode-Potential Potential Hydrogen Calomel Hydrogen Calomel .0001 .3275 -.3335 .6135 .0000 .2800 .0005 .3890 -.3615 .6415 4.0190 .2610 .001 .4230 -.3860 .6660 4.0300 .2500 .002 .5365 -.4340 .7140 4.0940 .1860 .004 .6720 -.5245 .8045 4.1530 .1270 .005 .7240 -.5500 .8300 4.1765 .1035 .006 .7575 -.5630 .8430 4.1920 .0880 .008 .8210 -.5995 .8795 4.2275 .0525 .01 .8790 -.6175 .8975 4.2615 .0185 .016 1.0580 -.7090 .9890 ---- -—-- -67.. TABLE LIV son-SLOT}. T‘TO o 3 1 CELL ANODE, AND CATHODE POTENTIAL DATA Temperature 2 50 0. pH : 3.0 (electrometric) Amperes Cell Cathode—Potential Anode-Potential Potential Hydrogen CalomBl' Hydrogen Calomel .0005 .2090 -.2990 .5790 -.1015 .3815 .001 .2648 -.3185 .5785 -.0795 .3595 .002 .3042 -.3315 .6115 -.0660 .3460 .004 .3800 -.3490 .6290 -.0475 .3275 .005 .4158 -.3635 .6435 -.0390 .3190 .006 .4430 -.3725 .6525 -.0385 .3185 .008 .4955 -.3820 .6620 -.0270 .3070 .01 .5425 -.3880 .6680 -.0255 .3055 .016 .6795 -.3995 .6795 -.0030 .2830 .02 .7580 -.4050 .6850 +.0010 .2790 .03 .9580 -.4115 .6915 4.0300 .2500 .04 1.1485 -.4220 .7020 4.0375 .2425 .06 1.5120 -.4310 .7110 4.0615 .2185 TABLE LV Solution No. 32 CELL, ANODE, AND CATHODE POTENTIA1.DATA Temperature 2 50° C. pH = 3.0 (electrometric) Amperes Cell’ Cathode-Potential Anode-Potential Potential Hydrogen Calomel' Hydrogen CalomSl .0001 .2340 -.3165 .5965 -.0880 .3680 .001 .2735 -.3240 .6040 -.0785 .3585 .002 .3150 -.3255 .6055 -.0580 .3380 .004 .3895 -.3380 .6180 -.O425 .3225 .006 .4560 -.3450 .6250 -.0300 .3100 .008 .5160 -.3585 .6385 -.0242 .3042 .01 .5960 -.3690 .6490 -.0145 .2945 .016 .7675 -.3885 .6685 4.0080 .2720 .02 .8755 -.4005 .6805 4.0175 .2625 .03 1.1440 -.4155 .6955 4.0395 .2405 .04 1.3950 -.4260 .7060 4.0585 .2215 -68- TABLE LVI Solution No. 33 CELL, ANODE, AND CATHODE POTENTIAL DATA Temperature 3 500 C. pH 2 3.0 (electrometric) Amperes 0611 Cathode-Patential Anode-Potential Potential Hydrogen Calomel Hydrogen Calom31 .0001 .2285 -.3050 .5850 -.0845 - .3645 .001 .2825 -.3195 .5995 -.0655 .3455 .002 .3425 -.3390 .6190 -.O500 .3300 .004 .4255 -.3600 .6400 -.0330 .3130 .006 .4985 -.3750 .6550 -.0210 .3010 .008 .5520 ~.3825 .6625 -.0130 .2930 .01 .6115 -.3875 .6675 -.0055 .2855 .016 .7742 -.4020 .6820 4.0135 .2665 .02 .8800 -.4080 .6880 4.0245 .2555 .03 1.1340 -.4205 .7005 4.0380 .2420 .04 1.3800 -.4290 .7090 4.0470 .2230 TABLE LVII Sdlution No. 34 CELL, ANODE,.AND CATHODE POTENTIAL.DATA Temperature 2 50° C. pH = 3.0 (electrometric) Amperes Cell Cathode-P6tential Anode-Potential Potential Hydrogen Calomel Hydrogen Calomel .0001 .1810 -.2580 .5380 -.0905 .001 .2302 -.2740 .5540 -.O795 .002 03540 “05755 06555 -00660 .004 .4820 -.4300 .7100 -.0500 .006 .5420 -.4345 .7145 -.0400 .008 .5972 -.4405 .7205 -.0300 .01 .6415 -.4405 .7205 -.0260 .016 .8290 -.4665 .7465 -.0050 .02 .9430 -.4810 .7610 4.0088 .03 1.2002 -.5062 .7862 4.0280 .04 1.4295 -.4865 .7665 4.0480 -69... 58355365383453); Jilin-5.2.5333 A33£v.u.8333513§ .335..§133§3 .36! 331-33 3333'! .o 0.0 «.0- = _ u «.0. «6 no? _ a q u d _ A q A .I 1.3“ 1 J A“ n.- n .n .l 1.2 n .I 10% n .8 a .— u 13 q I 1 .. 2 e. x T- 16; .u ' 40.“ W _ p _ _ b . p _ _ p _ _ _ p _ _ _ _ 38.35.536.953835833.3 Jot.8:33.».o.o.R..»I;3.-.o.£..s§§.n..alto Aifiivofinigggigg giaigailg.§ cane-lug .30-Si i i on? We 06 «.0- 101 bob. , q . . 1 _ _ .1 ea .I A M l N m. T N m m n 1 ca m .l .n u. m A l 3 N. l 0‘ q A u .l l a; W l. .n W p _ b p b _ _ _ — _ F — P P _ — _ P .2 5333 .n .8855 83.33 .c :3 6.3 3.13,. 38 3130 33.3 3 .83.. 3333; .6 £3. «a. __ __ 51o. 4.? q _ _ _ _ _ 1 o; l 2 o i ‘ A 'u'hmhllhnnmm-Io C G 6.2.333836.98833384.u.€33313.¢.850 .33333333.3 3383 'ufimu-hnhu-um 6.0.... on .383 c 6.3 i 3 .313 .- 83 .. a 338 .n 6.3 I a 338 .u 6.: a. on 33.. .. 6.: i on 338 .. :3 and.» 360 i3 3%! :0 .04.: Doug-«i O O .2 3 .3 ’u‘htNMIIAII-nm O 0 a v 0 “ .2. 8338 .o .8 3.38 .- .nn 333.... .. .855 “.3 58 3215.0 R 8 .256 33.2.6.3 3.3... .56: 31. 3 133... OJ 0 r: 'u'kMMnhw-auum gisia.ftiagd.£iogzi {tall—8...?!toga—tiniaakini.‘8:3 niaiiiigludl “jail—31.88.92 can!!! can“; ‘3. «.0 (G. q _ d u - J on H I CONN A h am 1 am a ,. 1 .. a x v. . a .u I 1 as N _. — _ — p P r — h p p h b p _ _ - _ _ .aiu'uig .03-333339.13": .< Sir-6 douse-«3.136 .oabnaou'aiadxfnn'nng 33.8 .filigiggigfig .ig‘igagigdg 335313.. 3383...... «a 3. — _ # L ~l n N .4 'u'bsaauntvunmwaa Paus.353.0.£ifi'§d.€iaii.g 3.9.382.ng gigging Pniiiilgfiét Salli Salli 3 c6 3 3 3. fl T4 . . _ q . q q _ _ 3 I 3 3 3: 3 ‘t H 'u‘kmmnhmm l I 3 l l Mfluunm“ l I In: I .4 p p p _ p _ P p F b _ p _ _ p _ giagdsfiiaia 2.338.usalad-3".ait.a§.p§q.o§laga.=lqlg.i PR'...SII¢:88.RI~I«I—..d.o.ttslaln8.:8.io {iiiniolilloiit . liggaédl .8383! 1 OJ I. I. _ _ u q _ l.. V. .. l l 3 T 1 3 I l 3 I l ‘u'ficumnhmm I I 3 u... .. . 8:3... 4.. 5.3 a. o .35.... .u 5.3 i a .538 .- 6... 8 . I138 .< 3.55 Ila 13.3.. 3.1.31.8 Illa .34! £~8.S.In....a_u.98.34133.u.o.88.3.§6.u.r8.8.6.8 .. 8250 gidiillioég 03 o.“ 'u-bcm-Mvnnvmoma 83.3.3.8... 33:313.. 3 od *8 q — _ _ — _ _ .l [and I 7 ad m .l n a u u w I J... I o s... . _ p r _ _ _ . _ . . . b no: o.3'«3u.nl.u.8i£'aiuon .n {ainnidhfnn‘gtouii 8.9825.31.J.u.o.3ungd.£8.~l.13..lllo FR32.338.182£253.u.£18l§38.8383.3§4.3.56 gal-3.419.933; ‘33:.td! 3353!. 3233'! 3 o..— 3 c. _ a... 3 .6 .1. «.o . . . . . . . q . . . . . . .x\ .l . .\ led I . . I°O~m ' n I... n u _ . . a 103 M .l a m . ’0.“ l a n. 4 L . _ _ . . . p p . . . . OJ o.~ 0“ '5: m «at: I: hut-a was DISCUSSION OF RESULTS The reproducibility of potential curves obtained in this experiment is none too good. The values obtained depend upon several variables such as the variation in the roughness and structure of the anode and cathode with change in current density, the distance between the electrodes, and with variations in the convection currents in the vicinity of the electrodes. Further- more, it is quite evident that the curves could be displaced con- siderably by a variation in the size of the cell or electrodes. However, since most of the variables were maintained constant throughout this investigation, the results should provide a good means for studying the comparative effects of the addition agents on current density - potential curves. It is to be understood, however, that no specific measurement can be considered as a con- stant reproducible value, for even with seemingly constant condi- tions, the author found that the results varied : 15 - 20%. The disucssion of this phase of the problem shall be con- cerned solely with an evaluation of the increase or decrease in the potential curves. As was mentioned in the introduction, the author has no intentions of explaining the curves in the light of other related plating problems. In the following discussion it will be noted that the author mentions a decrease or increase in the anodic or cathodic curves. An increase in the cathodic curve signifies a shift to a more -70- negative potential, whereas an increase in the anodic curve signi- fies a shift to a more positive potential. A decrease in either curve indicates the exact opposite effect. Watts Bath Figure 43 merely shows the effect of temperature on the stand- ard'watts bath (solution 7) and substantiates the already well known fact that an increase in temperature makes the cathodic curve less negative and the anodic curve less positive. Figure 44 indi- cates that the addition of benzene sulfonamide to the standard bath decreases the cathodic curve throughout the current density range. The anodic curve is also decreased above .5 amperes per sq. ft. Figure 44 also shows that the addition of sodium.o-benzoyl sulfimide to the standard solution (curve B), or the addition of both Class I compounds to the standard bath (curve A) increase the cathodic and anodic curves at 500 C., with the effect of the latter compounds somewhat greater on the cathodic curve. Figure 54 shows that temperature is of some importance in discussing the effects of these addition agents on the potential curves. There is little significant difference in the comparative effect on the anode at 50° c. or at 75° c. Solution 12 containing both Class I addition agents has little effect on the cathodic curve at 75°C. whereas it caused a slight increase at 50° C. Solution 9 containing only sodium.o-benzoyl sulfimide as an addition agent, slightly de- creased the standard cathodic curve from .5 - 3.5 amperes per sq. ft. inclusive at 750 C. in contrast to the slight increase at 50°C. -71- This indicates that the polarization effect of the sodium 0- benzoyl sulfimide at 50° c. is nullified by the increased tem- perature. Figure 55 shows that solution 9 and solution 12 increase the cell potential approximately the same, whereas solution 11 containing benzene sulfonamide increases the voltage at current densities above 1.5 amperes per sq. ft. Figure 45 clearly indicates that zinc has practically no effect on the curves. However, zinc in a concentration of .1 g./l. appears to have a very slight increasing effect on both the anode and cathode curves. Curve C, Figure 56, also shows that zinc has no effect on the cell potentials. The differences were too slight to graph, and thus it was convenient to show the effect of all three concentrations of zinc as one curve. Figure 46 indicates that the anodic and cathodic curves are decreased by the addi- tion of benzene sulfonamide to zinc, and furthermore curves A and E, Figure 56, also ShOW'a decrease in cell voltage for any specific current density. Figure 47 (curve B) indicates that PQ increases both the anodic and cathodic curves, and this effect, especially on the cathode, is more pronounced than.with the other addition agents investigated. Curve A further indicates that the addition of sodium o-benzoyl sulfimide and benzene sulfona- mide to PQ increases both curves to a slight extent. The cell voltage is somewhat increased by the addition of PQ and slightly more so when the Class I addition agents are present, as can be -72- noted by inspecting curves D and E in Figure 56. The effect of these Class I compounds is also more noticeable with increase in current density. High Chloride Bath Figure 48, shows substantially the same effect of temperature on the standard High Chloride bath as was shown on the standard watts bath in Figure 43. The anodic and cathodic curves of the former bath, however, are decreased over those of the latter at corresponding temperatures. An increase in temperature is, fur- thermore, directly related to a decrease in cell voltage as can be seen from an inspection of Figure 58. The addition of benzene sulfonamide to the standard bath has little effect at 25° C. as shown by curves A and B, Figure 49, but at 50° C., the cathodic curve is decreased somewhat at all current densities. Curves C and D, figure 49, also indicate that sodium o-benzoyl sulfimide alone or in combination with benzene sulfonamide tends to in- crease the cathodic curve. This is directly analogous to the effect shown by the same compounds in the Watts bath. Sodium o-benzoyl sulfimide increases the anodic curve, whereas little effect is noticed when benzene sulfonamide is also present. It is, thus, further seen that benzene sulfonamide has a tendency toward decreasing the curves. Zinc plus both Class I compounds increase the anode and cathode potentials above 1 ampere per sq. ft., but the concentration of zinc seemingly has no effect, as can -73- be seen by inspecting Figure 50. The cell voltage, is definitely increased for any current density, however, when zinc and the Class I compounds are present in the standard bath. Although the concentration of zinc is not too important, the higher concentra- tion shows the greatest effect. Chloride Bath Figure 51 again substantiates the temperature effect on the potential curves. At 50° c. and 75° C., the cathodic potentials are decreased in comparison with the corresponding curves of the High Chloride bath. At 25° C., however, there is little notice- able difference. The anodic curves are approximately the same for both solutions. This fact is rather interesting because it seems logical to predict that the additional chloride should have an enhanced corrosive effect thus decreasing the anodic curves. The only plausible explanation is that the chloride ion has an optimum concentration in its effect on the anode, and this concen- tration is realized in the High Chloride bath. Curve C, Figure 52, shows that benzene sulfonamide has no effect on either the anode or cathode curves. Sodium o—benzoyl sulfimide or both Class I compounds together, curves B and A respectively, effect an increase in the cathodic curves, with the latter showing a somewhat greater effect above 2 amperes per sq. ft. and a lesser effect below this current density. The anode curve is increased by solution 4 containing both addition agents, whereas solution -74... 2 containing sodium o-benzoyl sulfimide increases the potential below'l.5 amperes per sq. ft. and decreases it above this current density. The decreasing effect of the benzene sulfonamide thus appears to be limited in this all chloride bath to the lower cur- rent densities. Sulfate Bath The curves for the standard Sulfate bath in Figure 53 indi- cate clearly the necessity of the chloride ion in nickel solu- tion. Data was not obtained at higher current densities because the high resistance of the bath caused the voltage to exceed the limit of the potentiometer at very low currents. The effect of temperature is the same in this bath as in all others investi- gated, but the anodic and cathodic curves are greatly increased over those of any other bath. The presence of both Class I addi- tion agents decreased the cathodic curve below 2.5 amperes per sq. ft. and had little effect above. The anodic curve was in- creased quite a bit below 1 ampere per sq. ft. CONCLUSIONS It is apparent from the discussion and from an inspection of Figures 43-54 inclusive that the addition agents studied have little effect on the anodic and cathodic potentials. The inability of the author, as well as other investigators, to ‘ reproduce potential curves makes it difficult to establish any definite conclusions. However, in general, the addition agents show the followdng effects on the standard baths: 1. 2. 3. 4. Benzene sulfonamide has little effect but has a tendency to decrease the anodic and cathodic curves. Sodium o-benzoyl sulfimide, on the other hand, effects a slight increase in the potentials. The one exception was in the Watts bath at 75°C., where a slight decreasing effect was noticed. The Class I addition agents together cause an increase in the potentials, but a somewhat less effect than when sodium o-benzoyl sulfimide is used alone. Zinc, by itself, has the least effect of any addition agent investigated, causing practically no change in the standard bath potentials. The effect of concentration is also negli- gible. 5. A combination of zinc and benzene sulfonamide, however, effects a decrease in the anodic and cathodic potentials, illustrating once again the decreasing effect of the benzene sulfonamide. Furthermore, this combination of addition agents is the only ' one that causes a decrease in cell voltage in the standard Watts bath. 6. Zinc is not used alone in-the High Chloride bath but in com- .bination with both Class I addition agents, it causes an in- crease in all potential measurements. Thus it is concluded that zinc has more of an effect in the High Chloride bath than in the Watts bath. Furthermore, in the former bath, an increase in concentration causes an increase in the cell volt- age for any particular current density. 7. PQ increases the potential measurements more than any other one addition agent investigated. This effect, however, is further enhanced by combining with the Class I compounds. 8. The already well known temperature effect was substantiated in that an increase in temperature decreases the anodic and cathodic curves and decreases the voltage necessary to cause any specific current to flow across the cell. Furthermore, although no intensive temperature effect was studied, it is the opinion of the author that, in general, the addition agents behave similarily at any temperature. 9. Although not directly connected with this investigation, the author substantiated the effect of the chloride ion in re- ducing the abnormal anodic potential produced in a pure sul- fate nickel bath. -77.. l. 2. 3. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. LITERATURE CITED Ballay, n - Compt. rend. 199, 60-2 (1934) Blum,‘W. and Hogaboom, G., - "Principles of Electroplating and Electroforming", J. Wiley and Sons, Inc., NeW'York, 102-109, 1930. Dorrance, R. T. and Gardiner, - Trans. . Electrochem. Soc. 54, 303-312 (1928) Haas, J. Jr., - Vonthly Rev. Am. Electroplaters Soc. 4, No. 12, 4-8 (1917) Haring, H. 3. - Trans. . Electrochem. Soc. 46, 107 (1924) Hendricks, J. A. - Trans. Am. Electrochem. Soc. 82, 113-131 (1942) "' Levine,'W. S. and Serfass, 3. J. - Monthly Rev. Am. Electro- platers Soc., Vol. 34, #4, 454-461 (1947) Linick, T. L., Metal Finishing 59, 611, 614 (1941) Keyer,'W. R. Proc. .. Electroplaters Soc. 29, 65-68 (1945) Nichol, P. A. and watts, O. P., Trans. Am. Electrochem. Soc. 48! 31-33 (1925) Pine, P. R., "The Electrochemical Society“, The Electro- chemical Society Inc. NeW'York, 273-274 (1942) Pinner, W} L., Soderberg, G. and Baker, 3. M., Trans. Elec- trochem. Soc., g9, 539—578 (1941) Proctor, C. H. - Metal Ind. lg, 57, (1915) Raub, a. and Wittum, M. - Metal Finishing gg, 315-317, 427- 432 (1940) Springer, R., - Oberflachentech, 14, 49-51 (1957) Stout, L. 3., - Monthly Rev. Am. Electroplaters Soc. 23, No. 6, 34-39 (1936) "' Thomas, W} E. and Blum, W. - Trans. Am. Electrochem. Soc. 25, 193-218 (1924) 18. 19. 20. 21. LITERATURE CITED (Cont'd.) Thompson, H. de K. - "Theoretical and Applied Electro- chemistry", The Vaclfillan Co., New York, 9, (1939) ‘Waite, V. H. - "The Electrochemical Society", The Elec- trochemical Society Inc., New York, 273-274 (1942) Watts, 0. P. - Monthly Rev. Am. Electroplaters Soc. 8, No. 3, 4-10 (1921) wesley, W. A. and Roehl, E. J. - Trans. Am. Electrochem. Soc. 86, 419-429, (1944) Young, C. B. - Proc. Am. Electroplaters Soc. 28, 124-32 (1940) “— ”0V ‘1 8 NCV 2 6 48 0:01 4 '43. F328 2 4 ‘49 a... 4 ’50 ‘EHstiiiv RY ‘.)iL2"‘T llHllllNlIH||||HIWIIIIIUIIIIHII¢Hl|IIIIIIHIHIHIHII 31293 02446 7346