CONTROL, ANALYSIS,

AND TESTING

CHEMICAL ANALYSIS OF PLATING SOLUTIONS

by Charles Rosenstein
AM.254 Ltd., Ho/on, lsraei

and Stanley Hirsch

Leeam Consultants Ltd., New Rochelle, N. Y

Plating solutions must be routinely analyzed in order to maintain the recommended bath
formulation and to preempt the occurrence of problems related to improper levels of bath
constituents. Contaminant levels in the solutions must also be monitored. Manufacturers of
plating systems establish optimum specifications to ensure maximum solution efficiency and
uniformity of deposits. The various factors that cause the concentrations of bath constituents
to deviate from their optimum values are as follows:

I. drag-out:
2. solution evaporation;
3. chemical decomposition; and
4. unequal anode and cathode efficiencies

A current efficiency problem is recognized by gradual but continuous changes in pH,

metal content, or cyanide content (see Table 1).
The techniques employed for the quantitative analysis of plating solutions are classified
as volumetric (titrimetric), gravimctric, and instrumental. Volumetric and grnvimetric
methods are also known as “wet” methods. The analyst must select the method that is best
suited and most cost effective for a particular application.
The wet methods outlined here are simple, accurate, and rapid enough for practically all
plating process control. They require only the common analytical equipment found in the
laboratory, and the instructions are sufficiently detailed for an average technician to follow
without any difficulty. The determination of small amounts of impurities and uncommon

Table I. Problems Caused by Unequal Anode and

Cathode Effkiencies

High pH High anode efficiency

Low pH High cathode efficiency
High metal content High anode ctfiaency
Low metal content High cathode eff~aency
Hl:h fret cyamde Low anode efficiency
Low free cyamde High anode efficiency

518
metals should be referred to a competent laboratory, as a high degree of skill and chemical
knowledge are required for the determination of these constituents.
Hull cell testing (see the section on plating cells elsewhere in this Guidehook) enables the
operator to observe the quality of a deposit over a wide current density range.

VOLUMETRIC METHODS

When titrants composed of standard solutions are added to a sample that contains a
component whose concentration is to be quantrtatively determined, the method is referred to
as a volumetric method. The component to be determined must react completely with the
titrant in stoichiometric proportions. From the volume of titrant required, the component’s
concentration is calculated. The simplicity, quickness, and relatrvely low cost of volumetric
methods make them the most widely used for the analysis of plating and related solutrons.
Volumetric methods involve reactions of several types: oxidation-reduction, acid-base,
complexation, and precipitation. Indicators are auxiliary reagents, which usually signify the
endpoint of the analysis. The endpoint can be indicated by a color change, formation of a
turbid solution, or the solubilization of a turbid solution.
Some volumetric methods require little sample preparation, whereas others may require
extensive preparation. Accuracy decreases for volumetric analyses of components found in
low concentrations, as endpoints are not as easily observed as with the components found in
high concentrations.
Volumetric methods are limited in that several conditions must be satisfied. Indicators
should be available to signal the endpoint of the titration. The component-trtrant reaction
should not be affected by interferences from other substances found in the solution.

GRAVIMETRIC METHODS

In gravimetric methods, the component being determined is separated from other

components of the sample by precipitatron, volatilir.ation, or electroanalytical means.
Precipitation methods are the most rmportant gravimetnc methods. The precipitate is uquallq
a very slightly coluble compound of high purity that contains the component. The weight of
the precipitate is determined after it is filtered from solution, washed, and dried. Gravimetric
methods are used to supplement the available volumctrlc methods.
Limitations of gravimetric methods include the requirement that the precipitated
component has an extremely low solubihty. The precipitate must al\o be of high purity and
be easily filterable.
Species that are analyzed gravimetrically include chloride, sulfate, carbonate, phosphate,
gold, and silver.

INSTRUMENTAL METHODS

Instrumental methods differ from wet methods in that they measure a physical property
related to the composition of a rubstance, u herear wet methods rely on chemical reactmns.
The selection of an instrument for the analysis of plating solutions 15 a difficult task. Analysts
must decide if the cost is justified and if the analytical instrument is capable of analyzing for
the required substances with a high degree of accuracy and precision. Instruments coupled to
computers can automatically sample, analyze, and record results. Mathematical errors are
minimized and sample measurements are more reproducible than with wet methods.
Instrumental methods are also extremely rapid when compared with wet method<.
Unlike humans, instruments cannot judge. They cannot recognire improper sample
preparation or interfering substances. Erroneous results are sometimes produced by electronic
and mechanical malfunctions.

519
 Analytical instruments frequently used in the analysis of plating solutions can be
categorized as spectroscopic. photometric, chromatographic, and electroanalytical. Spectro-
scopic methods (flame photometry, emission spectrometry, X-ray fluorescence, mass spec-
trometry. and inductively coupled plasma) are based on the emission of light. Photometric
methods (spectrophotometry, calorimetry, and atomic absorption) are based on the absorption
of light. Chromatographic methods (ion chromatography) involve the separation of substance\
for subsequent identification. Electroanalytical methods (potentiometry. conductometry,
polarography, amperometry. and electrogravimetry) involve an electric current in the course
of the analysis.
The instrumental methods. comprehensively reviewed below. are most applicable to
plating environments.

SPECTROSCOPIC METHODS

Spectroscopy is the analysis of a substance by the measurement of emitted light. When

heat. electrical energy, or radiant energy is added to an atom, the atom becomes excited and
emits light. Excitation can be caused by a flame. spark, X-rays, or an AC or DC arc. The
electrons in the atom are activated from their ground state to unstable energy shells of higher
potential energy. Upon returning to their ground state, energy is released in the form of
electromagnetic radiation.
Because each element contains atoms with different arrangements of outermost elec-
trons, a distinct set of wavelengths is obtained. These wavelengths, from atoms of several
elements, are separated by a monochromator such as a prism or a diffraction grating.
Detection of the wavelengths can be accomplished photographically (spectrograph) or via
direct-reading photoelectric detectors (spectrophotometers). The measurement of intensity
emitted at a particular wavelength is proportional to the concentration of the element being
analyzed.
An advantage of spectroscopy is that the method is specific for the element being
analyzed. It permits quantitative analysis of trace elements without any preliminary treatment
and without prior knowledge as to the presence of the element. Most metals and \ome
nonmetals may be analyzed. Spectroscopic analysis is also useful for repetitive analytical
work.
Disadvantages of spectroscopic analysis include the temperature dependence of intensity
measurements, as intensity is very sensitive to small fluctuations in temperature. The accuracy
and precision of spectrographic methods is not as high as some spectrophotometric methods
or wet analyses. Spectrographic methods are usually limited to maximum element concen-
trations of 3%. Additionally, semitivity is much smaller for elements of high energy (e.g..
zinc) than for elements of low energy (e.g., sodium).
Applications of spectroscopy include the analysis of major constituent!, and impurities in
plating solutions, and of alloy deposits for composition.

Flame Photometry
In flame photometry (FP), a sample in solution is atomized at constant air pressure and
introduced in its entirety into a flame as a fine mist. The temperature of the flame
(1,800-3,100-K) is kept constant. The solvent is evaporated and the solid is vaporized and
then dissociated into ground state atoms. The valence electrons of the ground state atoms are
excited by the energy of the flame to higher energy levels and then fall back to the ground
state. The intenhitie\ of the emitted spectrum lines are determined in the spectrograph or
measured directly by a spectrophotometer.
The flame photometer is calibrated with standards of known composition and concen-
tration. The intensity of a given spectral line of an unknown can then be correlated with the
amount of an element present that emits the specific radiation.

520
 Physical interferences may occur from solute or solvent effects on the rate of transport
of the sample into the flame. Spectral interferences are caused by adjacent line emissions
when the element being analyzed has nearly the same wavelength as another element.
Monochromators or the selection of other spectral lines minimiLe this interference. Ionization
interferences may occur with the higher temperature flames. By adding a second ionizable
element, the interference< due to the ionization of the element being determined are
minimized.
An advantage of FP IS that the temperature of the flame can be kept more nearly constant
than with electric sources. A disadvantage of the method is that the sensitivity of the flame
wurce is many times smaller than that of an electric arc or cpark.
FP is used for the analysis of aluminum, boron, cadmium, calcmm, chromium, cobalt,
copper, indium, Iron, lead, lithium, magnesium, nickel, palladium, platinum, potassium.
rhodium, ruthenium, silver, sodium, strontium, tin, and rinc.

Emission Spectrometry
In emission spectrometry (ES), a sample composed of a solid, cast metal or solution 1s
ewclted by an electric discharge such as an AC arc, a DC arc, or a spark. The sample is usually
placed in the cavity of a lower graphite electrode, which 15 made positiv-e. The upper
counterelectrode is another graphite electrode ground to a point. Graphite is the preferred
electrode material because of Its abihty to withstand the high electric discharge temperatures.
It is also a good electrical conductor and does not generate its own spectral lines.
The arc is started by touching the two graphite electrodes and then separating them The
extremely high temperatures (J,OOGh,OOO“K) produce emitted radiation higher in energy and
in the number of spectral lines than in flame photometry. Characteristic wavelengths from
atoms of several elements arc separated by a monochromator and are detected hy \pectro-
graphs or ?pectrophotometers. Qualitative identifuxtion i\ performed by using available
charts and tables to identify the \pectrnl lines that rhe emission spectrometer sorts out
according to their wavelength. The elements present in a rample can alw he quahtatlcrly
determined by comparmg the spectrum of an unknown wnh that of pure samples of the
elements. The density of the wakelengths is proportional to the concenwatwn of the clement
being determined. Calibrations are done against standard samples.
ES is a useful method for the analysis of trdce metallic contdmmantr in plating barhu. Ihe
“oxide” method is a common quantitative technique in ES. A sample of the plating bath is
evaporated to dryness and then heated rn a muffle fwnace. The resultant oxides are mixed
with graphite and placed in a praphlte electrode. Stand,wds are Gmilarly prepared dnd a I)(
drc i5 used to excite the sample and Gandards.

X-ray Fluorescence
X-ray fluorescence o(N) qwctrosc~~py is baaed on the cxcltatlon of wnpler hq an
X-ray source of sufficiently high energy, resulting in the cmi<>ion of Iluorcsccnt r.ldiatmn.
lhe concentration of the element being determined IS proportional to the intsnsit> of ItS
chartcterihtic N avelength. A I) pical XRF q)ectrometcr consists of an X-ray ~owcc. ;I detector,
and a data analyzer.
Advantagr~ of XRF include the nondestructive nature *If the X-ray\ on the tample. XRF
is useful in measuring the major constituents of platrng baths wch ;I- cadmium. chrommm.
cobalt, gold, nickel, silver, tin, and lint. I>~~ad\:cnta~es of ?rRF ~ncludc its lack of wn\itl\tt)
as compared with ES.
X-ray spectroscopy ih alw used to measure the thichnetr of a plated deposit. ‘The X-ray
detector is placed on the wavelength of the element bring meawred. rhe surface of the
deposit is exposed to an X-ray source and the intensity of the element ~a\rlrngth is measured.
A calibration cur\e is cowtructed for intensity against thickness for a particular deposit.
Coating compositions can also be determined by XRF.

522
Mass Spectrometry
In mass spectrometry (MS), gases or vapors derived from liquids or solids are bombarded
by a beam of electrons in an ionization chamber, causing ionization and a rupture of chemical
bonds. Charged particles are formed, which may be composed of elements, molecules, or
fragments. Electric and magnetic fields then separate the ions according to their mass to
charge ratios (m/r). The amount and type of fragments produced in an ionization chamber. for
a particular energy of the bombarding beam, are characteristic of the molecule; therefore,
every chemical compound has a distinct mass spectrum. By establishing a mass spectrum of
several pure compounds, an observed pattern allows identification and analysis of complex
mixtures.
The mass spectrum of a compound contains the masses of the ion fragments and the
relative abundances of these ions plus the parent ion. Dissociation fragments will always
occur in the came relative abundance for a particular compound.
MS is applicable to all substances that have a sufficiently high vapor pressure. This
usually includes substances whose boiling point is below 450°C. MS permits qualitative and
quantitative analysis of liquids, solids, and gases.

Inductively Coupled Plasma

Inductively coupled plasma (ICP) involves the aspiration of a sample in a stream of
argon gas, and then its ionization by an applied radio frequency field. The field is inductively
coupled to the ionized gas by a coil surrounding a quartz torch that supports and encloses the
plasma. The sample aerosol is heated in the plasma, the molecules become almost completely
dissociated and then the atoms present in the sample emit light at their characteristic
frequencies. The light passes through a monochromator and onto a detector.
The high temperature (7,OOO”K) of the argon plasma gas produces efficient atomic
emission and permits low detection limits for many elements. As with atomic absorption
(AA), ICP does not distinguish between oxidation states (e.g., Cr” and Crhi) of the same
element-the total element present is determined. Advantages of ICP include complete
ionization and no matrix interferences as in AA. ICP allows simultaneous analysis of many
elements in a short time. It is sensitive to part-per-billion levels.
Disadvantages of ICP include its high cost and its intolerance to samples with greater
than 3% dissolved solids. Background corrections usually compensate for interferences due to
background radiation from other elements and the plasma gases. Physical interferences, due
to viscosity or surface tension, can cause significant errors. These errors are reduced by
diluting the sample. Although chemical interferences are insignificant in the ICP method, they
can be greatly minimized by careful selection of the instrument’s operating conditions. by
matrix matching, or by buffering the sample.
ICP is applicable to the analysis of major components and trace contaminant, in plating
solutions. It is also useful for waste-treatment analysis.

PHOTOMETRIC METHODS

Photometric methods are based on the absorption of ultraviolet (200-400 nm) or visible
(400-1,000 nm) radiant energy by a species in solution. The amount of energy absorbed is
proportional to the concentration of the absorbing species in solution. Absorption is
determined spectrophotometrically or calorimetrically.
The sensitivity and accuracy of photometric methods must be frequently checked by
testing standard solutions in order to detect electrical, optical, or mechanical malfunctions in
the analytical instrument.

523
Spectrophotometry and Colorimetry
S~~e~rropllotonzer~~ involves analysis by the measurement of the light absorbed by a
solution. The absorbance is proportional to the concentration of the analyte in solution.
Spectrophotometric methods are most often used for the analysis of metals with concentra-
tions of up to 2%.
Spectrophotometers consist of a light source (tungsten or hydrogen), a monochromator,
a sample holder, and a detector, Ultraviolet or vjisible light of a definite wavelength is used
as the light source. Detectors are photoelectric cells that measure the transmitted (unabsorbed)
light, Spectrophotometers differ from photometers in that they utilirc monochromators.
whereas photometers use filters to isolate the desired wavelength region. Filter\ isolate a
wider band of light.
In spectrophotometric titrations, the cell containing the analyte solution is placed in the
light path of a spectrophotometer. Titrant is added to the cell with stirring. and the absorbance
is measured. The endpoint is determined graphically. Applications of this titration include the
analysis of a mixture of arsenic and antimony and the analysis of copper with ethylene
diamine tetra acetic acid (EDTA).
The possibihty of errors in spectrophotometric analyses is increased when numerous
dilutions are required for an analysis.
Colorirner~~ involves comparing the color produced by an unknown quantity of a
substance with the color produced by a standard containing a known quantity of that
substance. When monochromatic light passes through the colored solution, a certain amount
of the light, proportional to the concentration of the substance, will be absorbed. Substances
that are colorless or only slightly colored can he rendered highly colored by a reaction with
special reagents.
In the standard series calorimetric method. the analytc solution is diluted to a certain
volume (usually 50 or I00 ml) in a Ncsslcr tube and mixed. The color of the solution is
compared with a series of standards similarly prepared. The concentration of the analyte
equals the concentration of the standard solution whose color it matches exactly. Colors can
also be compared to standards via a colorimctcr (photometer), comparator. or apcctropho-
tometer.
The possible errors in calorimetric measurements may arise from the following sources:
turbidity, sensitivity of the eye or color blindness, dilutions. photometer filter\. chemical
interferences, and variation\ in temperature or pH.
Photometric methods arc available for the analysis of the following analytes:

Anodizing solutions: Fe, Cu. Mn

Brass solutions: Fe
Cadmium solutions: Fe, Ti. Zn. Cu. Ni
Chromium solutions: Cr, Fe, Ni, Cu, SC
Acid copper solutions: Cl, Fe
Alkaline copper solutions: Fe, Se
Gold solutions: Au. Ni, In, Co. Cu, Fe, PO,
Iron solutions: Mn, NH,
Lead and tin-lead solutions: Pb
Nickel solutions: Cr. Cu. Zn, Fe. Co, NH,
Palladium solutions: Pd. Cr. NH,
Platinum solutions: Pt
Rhodium solutions: Rh
Silver solutions: Ni. Cu. Sb
Acid tin solutions: Fe. Cu
Alkaline tin solution\: Cu. Pb, Zn

524
 Acid zinc solutions: Cu. Fe
Alkaline zinc solutions: Cu, Fe
Wastewater: Ohi. Ni, Cu, Fe, Zn, Ph. Al, B, NO,, NO?, PO,. Cl. CN, wetting agents.

Atomic Absorption
Metals in plating and related solutions can be readily determined by AA spectropho-
tometry. Optimum ranges, detection limits, and sensitivities of metals vary with the various
available instruments.
In dire&os@rrtiort atontic crb.sor/,tiort (DAAA) analysis, the flame (usually air-
acetylene or nitrous oxide-acetylene) converts the sample aerosol into atomic vapor. which
absorbs radiation from a light source. A light source from a hollow cathode lamp or an
electrodeless discharge lamp is used, which emits a spectrum specific to the element being
determined. The high cost of these lamps is a disadvantage of the AA method. A detector
measures the light intensity to give a quantitative determination.
DAAA is similar to flame photometry in that a sample is aspirated into a flame and
atomized. The difference between the two methods is that tlame photometry measures the
amount of emitted light. whereas DAAA measures the amount of light absorbed by the
atomized element in the flame. In DAAA. the number of atoms in the ground state is much
greater than the number of atoms in any of the excited states of the spectroscopic methods.
Consequently, DAAA is more efficient and has better detection limits than the spectroscopic
methods.
Spectral interferences occur when a wavelength of an element being analyzed is close to
that of an interfering element. The analysis will result in an erroneously high measurement.
To compensate for this interference, an alternate wavelength or smaller slit width is used.
When the physical properties (e.g.. viscosity) of a sample differ from those of the
standard, matrix interferences occur. Absorption can be enhanced or suppressed. To overcome
these interferences, matrix components in the sample and standard are matched or a release
agent, such as EDTA or lanthanum, is added.
Chemical interferences are the most common interferences encountered in AA analysis.
They result from the nonabsorption of molecularly bound atoms in the flame. These
interferences are minimized by using a nitrous oxide-acetylene flame instead of an
air-acetylene flame to obtain the higher flame temperature needed to dissociate the molecule
or by adding a specific substance (e.g., lanthanum) to render the interferant harmless.
Chemical interferences can also be overcome by extracting the element being determined or
by extracting the interferant from the sample.
The sensitivity and detection limits in AA methods vary with the instrument used, the
nature of the matrix, the type of element being analyzed, and the particular AA technique
chosen. It is best to use concentrations of standards and samples within the optimum
concentration range of the AA instrument. When DAAA provides inadequate sensitivity.
other specialized AA methods, such as graphite fur-nace AA, cold vapor AA, or hydride AA.
are used.
In ~rr@n’tr furnace AA (GFAA). the flame that is used in DAAA is replaced w’ith an
electrically heated graphite furnace. A solution of the analyte is placed in a graphite tube in
the furnace, evaporated to dryness, charred, and atomized. The metal atoms being analyzed
are propelled into the path of the radiation beam by increasing the temperature of the furnace
and causing the sample to bc volatilized. Only very small amounts of sample are required for
the analysis.
GFAA is a very sensitive technique and permits very low detection limits. The increased
sensitivity is due to the much greater occupancy time of the ground state atoms in the optical
path as compared with DAAA. Increased sensitivity can also be obtained by using larger
sample volumes or by using an argon-hydrogen purge gas mixture instead of nitrogen,
Because of its extreme sensitivity. determining the optimum heating times. temperature. and
matrix modifiers is necessary to overcome possible interferences.

526
 Interferences may occur in GFAA analysis due to molecular absorption and chemical
effects. Background corrections compensate for the molecular absorption interference.
Specially coated graphite tubes minimize its interaction with some elements. Gradual heating
helps to decrease background interference, and permits determination of samples with
complex mixtures of matrix components.
The GFAA method has been applied to the analysis of aluminum, antimony, arsenic,
barium, beryllium, cadmium, chromium, cobalt, copper, iron, lead, manganese, molybdenum,
nickel, selenium, silver, and tin.
Cold vapor atomic absorprion (CVAA) involves the chemical reduction of mercury or
selenium by stannous chloride and its subsequent analysis. The reduced solution is vigorously
stirred in the reaction vessel to obtain an equilibrium between the element in the liquid and
vapor phases. The vapor is then purged into an absorption cell located in the light path of a
spectrophotometer. The resultant absorbance peak is recorded on a strip chart recorder.
The extremely sensitive CVAA procedure is subject to interferences from some organics,
sulfur compounds, and chlorine. Metallic ions (e.g., gold, selenium), which are reduced to the
elemental state by stannous chloride, produce interferences if they combine with mercury.
Hydride atomic absorpfion (HAA) is based on chemical reduction with sodium
borohydride to selectively separate hydride-forming elements from a sample. The gaseous
hydride that is generated is collected in a reservoir attached to a generation flask, and is then
purged by a stream of argon or nitrogen into an argon-hydrogen-air flame. This permits
high-sensitivity determinations of antimony, arsenic, bismuth, germanium, selenium, tellu-
rium, and tin.
The HAA technique is sensitive to interferences from easily reduced metals such as
silver, copper, and mercury. Interferences also arise from transition metals in concentrations
greater than 200 mg/L and from oxides of nitrogen.

Ion Chromatography
In ion chromatography (IC), analytes are separated with an eluent on a chromatographic
column based on their ionic charges. Because plating solutions are water based, the soluble
components must be polar or ionic; therefore, IC is applicable to the analysis of plating and
related solutions.
Ion chromatographs consist of a sample delivery system, a chromatographic separation
column, a detection system, and a data handling system.
IC permits the rapid sequential analysis of multiple analytes in one sample. The various
detectors available, such as W-visible, electrochemical, or conductivity, allow for specific
detection in the presence of other analytes. IC is suitable for the analysis of metals, anionic
and cationic inorganic bath constituents, and various organic plating bath additives. It is also
used for continuous on-line operations.
Interferences arise from substances that have retention times coinciding with that of any
anion being analyzed. A high concentration of a particular ion may interfere with the
resolution of other ions. These interferences can be greatly minimized by gradient elution or
sample dilution.
IC has been applied to the analysis of the following analytes in plating and related
solutions:
Merals: Aluminum, barium, cadmium, calcium, trivalent and hexavalent chromium,
cobalt, copper, gold, iron, lead, lithium, magnesium, nickel, palladium, platinum, silver, tin,
zinc.
Ions: Ammonium, bromide, carbonate, chloride, cyanide, fluoborate, fluoride, hypophos-
phite, nitrate, nitrite, phosphate, potassium, sodium, sulfate, sulfide, sulfite.
Acid Mixtures: Hydrofluoric, nitric, and acetic acids.
Organics: Brighteners, surfactants, organic acids.

527
 ELECTROANALYTICAL METHODS

Electroanalytical methods involve the use of one or more of three electrical

quantities+urrent, voltage, and resistance. These methods are useful when indicators for a
titration are unavailable or unsuitable. Although trace analysis may be done quite well by
spectroscopic or photometric methods, electroanalytical methods offer ease of operation and
relatively lower costs of purchase and maintenance.

Potentiometry
Potentiometry involves an electrode that responds to the activity of a particular group of
ions in solution. Potentiometric methods correlate the activity of an ion with its concentration
in solution.
In potentiometric titrations, titrant is added lo a solution and the potential between an
indicator and reference electrode is measured, The reaction must involve the addition or
removal of an ion for which an electrode is available. Acid-base titrations are performed with
a glass indicator electrode and a calomel reference electrode. The endpoint corresponds to the
maximum rate of change of potential per unit volume of titrant added.
Advantages of potentiometric titration5 include irs applicability to colored. turbid, or
fluorescent solutions. It is also useful in situations where indicators are unavailable.
The sensitivity of potentiometric titrations is limited by the accuracy of the measuxment
of electrode potentials at low concentrations. Solutions that arc more dilute than 10 ’ N
cannot be accurately titrated potentiometrically. This is because the experimentally measured
electrode potential is a combined potential. which may differ appreciably from the true
electrode potential. The difference between the true and experimental electrode potentials ia
due to the residual current. which arises from the presence of electroactive trace impurities.
The direct potentiometric measurement of single ion concentrations is done with ion
selective electrodes (ISEa). The ISE develops an electric potential in response to the activity
of the ion for which the electrode is specific. ISEs are available for measuring calcium,
copper, lead, cadmium, ammonia, bromide, nitrate, cyanide, sulfate, chloride, fluoride, and
other cations and anions.
Cation ISEs encounter interferences from other cations, and anion ISEs encounter
interferences from other anions. Theae interferences can be eliminated by adjusting the sample
pH or by chelating the interfering ions. ISE instructions must be reviewed carefully to
determine the maximum allowable levels of interferants, the upper limit of the single ion
concentration for the ISE, and the type of media compatible with the particular ISE.
Some of the solutions that can be analyzed by potentiometric methods are:

Anodizing solutions: Al, H$O,, CIHLOJ. CrO,, Cl

Brass solutions: Cu, Zn, NH,, CO,
Bronze solutions: Cu. Sn. NaOH, NaCN, Na&O,
Chromium solutions: Cr, Cl
Cadmium solutions: Cd, NaOH. NaCN, Na?CO,
Acid copper solutions: Cl
Alkaline copper solutions: NaOH, NaCN, Na&O,
Gold solution,: Au. Ag. Ni. Cu
Lead and tin/lead solutions: Ph. Sn, HBF,
Nickel solutions: Co. Cu, Zn. Cd, Cl. H,BO,
Silver solutions: Ag, Sb, Ni
Acid tin solutions: Sn. HBF,, H,SO,
Alkaline tin aolutiona: Sn, NaOH. NaCO,. Cl
Zinc solutions: Zn

528
Conductometry
Electrolytic conductivity measures a solution’s ability to carry an electric current. A
current is produced by applying a potential between two inert metallic electrodes (e.g.,
platinum) inserted into the solution being tested. When other variables are held constant,
changes in the concentration of an electrolyte result in changes in the conductance of electric
current by a solution.
In conductometric titrations, the endpoint of the titration is obtained from a plot of
conductance against the volume of titrant. Excessive amounts of extraneous foreign
electrolytes can adversely affect the accuracy of a conductometric titration.
Conductometric methods are used when wet or potentiometric methods give inaccurate
results due to increased solubility (in precipitation reactions) or hydrolysis at the equivalence
point. The methods are accurate in both dilute and concentrated solutions, and they can also
be u5ed with colored solutions.
Conductometric methods have been applied to the analysis of Cr. Cd, Co, Fe, Ni, Pb, Ag,
Zn, CO,, Cl, F, and SO,.

Polarography
In polarography, varying voltage is applied to a cell consisting of a large mercury anode
(reference electrode) and a small mercury cathode (indicator electrode) known as a dropping
mercury electrode (DME). Consequent changes in current are measured. The large area of the
mercury anode precludes any polarization. The DME consists of a mercury reservoir attached
to a glass capillary tube with small mercury drops falling slowly from the opening of the tube.
A saturated calomel electrode is sometimes used as the reference electrode.
The electrolyte in the cell consists of a dilute solution of the species being determined in
a medium of supporting electrolyte. The supporting electrolyte functions to carry the current
in order to raise the conductivity of the solution. This ensures that if the species to be
determined is charged, it will not migrate to the DME. Bubbling an inert gas, such as nitrogen
or hydrogen, through the solution prior to running a polarogram, will expel dissolved oxygen
in order to prevent the dissolved oxygen from appearing on the polarogram.
Reducible ions diffuse to the DME. As the applied voltage increases, negligible current
flow results until the decomposition potential is reached for the metal ion being determined.
When the ions are reduced at the same rate as they diffuse to the DME, no further increases
in current occur, as the current is limited by the diffusion rate. The half-wave potential is the
potential at which the current is 50% of the limiting value.
Polarograms are obtained by the measurement of current as a function of applied
potential. Half-wave potentials are characteristic of particular substances under specified
conditions. The limiting current is proportional to the concentration of the substance being
reduced. Substances can be analyzed quantitatively and qualitatively if they are capable of
undergoing anodic oxidation or cathodic reduction. As with other instrumental methods,
results are referred to standards in order to quantitate the method.
Advantages of polarographic methods include their ability to permit simultaneous
qualitative and quantitative determinations of two or more analytes in the same solution.
Polarography has wide applicability to inorganic, organic, ionic, or molecular species.
Disadvantages of polarography include the interferences caused by large concentrations
of electropositive metals in the determination of low concentrations of electronegative metals.
The very narrow capillary of the DME occasionally becomes clogged.
Polarographic methods are available for the following solutions:

Anodizing solutions: Cu, Zn, Mn

Brass solutions: Pb, Cd, Cu, Ni, Zn
Bronze solutions: Pb, Zn, Al, Cu. Ni
Cadmium solutions: Cu, Pb, Zn, Ni

530
Table II. Reactions That Can Be Analyzed by Amperometry

Fluoride Lead mtrate Potassium chloride

Gold Hydroquinone Sulfuric acid
Nickel Dimethylglyoximc Chloride
Lead Sodium tluoride Chloride
Bromide Silver nmnte Nitric acid
CttlCilltll EDTA Ammonia
Cadmium EDTA Ammonia
Chloride Silver nimte Nitric acid
EDTA Weak acid

Chromium solutions: Cu, Ni, Zn, Cl, SO,

Acid copper solutions: Cu. Cl
Alkaline copper solutions: Zn, Fe, Pb, Cu
Gold solutions: Au, Cu, Ni, Zn, In, Co, Cd
Iron solutions: Mn
Lead and tin-lead solutions: Cu, Cd, Ni, ‘Zn, Sb
Nickel solutions: Cu. Pb, Zn, Cd, Na, Co, Cr, Mn
Palladium solutions: Pd, Cr” , CT”+
Rhodium solutions: Rh
Silver solutions: Sb, Cu, Cd
Acid tin solutions: Sn4+, Cu, Ni, Zn
Alkaline tin solutions: Pb, Cd, Zn, Cu
Acid zinc solutions: Cu. Fe, Pb, Cd
Alkaline zinc solutions: Pb. Cd, Cu
Wastewater: Cd 1 Cu 3 Cr’+, Ni, Sn, Zn

Amperometry
Amperometric titrations involve the use of polarography as the basis of an electrometric
titration. Voltage applied across the indicator electrode (e.g., DME or platinum) and reference
electrode (e.g., calomel or mercury) is held constant and the current passing through the cell
is measured as a function of titrant volume added. The endpoint of the titration is determined
from the intersection of the two straight lines in a plot of current against volume of titrant
added. Polarograms are run to determine the optimum titration voltage.
Amperometric titrations can be carried out at low analyte concentrations at which
volumetric or potentiometric methods cannot yield accurate results. They are temperature
independent and more accurate than polarographic methods. Although amperometry is useful
for oxidation-reduction or precipitation reactions, few acid-base reactions are determined by
this method.
Some of the reactions that can be analyzed by amperometric methods are given in
Table II.

Electrogravimetry
In electrogravimetry, the substance to be determined is separated at a fixed potential on
a preweighed inert cathode, which is then washed, dried. and weighed. Requirements for an
accurate electrogravimetric analysis include good agitation, smooth adherent deposits, and
proper pH, temperature, and current density.

531
Table III. Molarities and Normalities of Standard Solutions

EDTA C,,,H,,0,N2Na2.?H,0
Ferrous ammonium xdt’atc FeSO,(NH,),SO,6H,O
Hydrochloric acid HCI
Iodine ‘2
Potaswm dichromatc K,Cr,O,
Potassium iodide-iodaw KILKl03
Potassium permanpanate KMnO,
Potassium thiocyanats KSCN
Silver nitrate AgNO,
Sodium hydroxide NaOH
Sodium thiosulfate Na&O,.SH,O
EDTA. rthylenr dl;*mlne tem dCr,l‘ :K,d.

Advantages of electrogravimetry include its ability to remove quantitatively most

common metals from solution. The method does not require constant supervision. Disadvan-
tages include long electrolysis times.
Some of the metals that have been determined clectrogravimetrically are cadmium.
cobalt, copper. gold, iron. lead. nickel, rhodium, silver. tin, and zinc.

SAMPLING

Analyses are accurate only when the sample is truly representative of the solution being
analyzed. Each tank should have a reference mark indicating the correct level for the solution,
and the bath should always be at this level when the sample is taken. Solutions should be
stirred before sampling. If there is sludge in the tank. the solution should be stirred at the end
of the day and the bath allowed to stand overnight, taking the sample in the morning.
Solutions should be sampled by means of a long glass tube. The tube is immersed in the
solution, the thumb is placed over the upper open end. and a full tube of solution is withdrawn
and transferred to a clean, dry container. The solution should be sampled at a minimum of IO
locations in the tank to ensure a representative sample. A quart sample is sufficient for
analysis and Hull cell testin g, and any remaining solution can be returned to its tank.

STANDARD SOLUTIONS, REAGENTS, AND INDICATORS

FOR WET METHODS

Standard solutions, reagents, and indicators can be purchased ready-made from labora-
tory supply distributors. Unless a laboratory has the experience and high degree of accuracy
that is required in preparing these solutions, it is recommended that they be purchased as
prepared solutions. Preparations for all the solutions are given here to enable technicians to
prepare or recheck their solution?.
A standard solution is a solution with an accurately known concentration of a substance
used in a volumetric analysis. Standardiration of standard solutions requires greater accuracy
than routine volumetric analyses. An error in standardization causes errors in all analyses that
are made with the solution: therefore. Primary Standard Grade chemicals should be used to
standardize standard solutions.
The strengths of standard solutions are usually expressed in terms of normality or
molarity. Normalities of standard solutions and their equivalent molarities are listed in Table
III. The methods to standardize all the standard solutions required for the analysis of plating
and related solutions are listed in Table IV.

532
 Indicators are added to solutions in volumetric analyses to show color change or onset of
turbidity, signifying the endpoint of a titration. The indicators required for all of the analyses and
their preparations are listed in Table V. Analytical Grade chemicals should be used in preparing
analytical reagents (Table VI) and Reagent Grade acids should be used (Table VII). When
chemicals of lesser purity are used, the accuracy of the results will be diminished.
Tables VIII through XII provide specific methods for testing the constituents of
electroplating. electroless. and anodizing baths, as well as acid dips and alkaline cleaners.

SAFETY

As with any laboratory procedure, the accepted safety rules for handling acids, bases, and
other solutions should be followed. Acids are always added to water. not the reverse. Mouth
pipettes should not be used for pipetting plating solutions. Safety glasses should always be
worn, and care should be exercised to avoid skin and eye contact when handling chemicals.
A fume hood should be used when an analytical method involves the liberation of harardoua
or annoying fumes. Laboratory staff should be well versed in the fir&t-aid procedures required
for various chemical accidents.

DETERMINATION OF CATHODE EFFICIENCY

The procedure for determining cathode efficiency, using the setup pictured in Fig. I, is
as follows:
I. Connect the copper coulometer in series with the test cell.
2. The copper coulometer solution should contain 30 or/gal copper sulfate pentahydrate
and 8 oz/gal sulfuric acid.
3. Use the same anodes, temperature, and agitation in the test solution that are used in
the plating bath.
4. Plate at 0.4 A (30 A/ft’) for a minimum of IO minutes.
5. Rinse both cathodes, dry in acetone, and weigh.
weight in gram5 of test metal X valence of test metal in bath X 3177
Ic Cathode Efficiency =
weight in grams of copper metal X atomic weight of test metal

Test Solution Copper Coulometer

Table IV. Standardization of Standard Solutions

Solu/io~i Rerr~c”” (To he rrddd ,,I ot-ckr li,\r~d) Trrrmr

0.1 M EDTA 5.0 8 CCO, dirwlved m I:3 HCI and diluted tu 500 ml in a EDTA Red-blue M EDTA = (WI CaCO,
37.0 B volumetric tlask. Pipette 20.ml rample, add 100 ml H,O, *’ IO ml x 1111\wlple)l
NalEDTA.2H,0 per pH IO hufferfer.and EBT powder. (ml EDTA X 50.05)
liter H,O
0.1 N HCI 0.2 0” Na2C0,. I25 ml H,O. and bromocresol green. HCI Blue-green N HCI = (M.t Na,CO,)/
Y ml 36% HCI per (IllI x 0.05299)
bter H,O
1.0 N HCI 2 0 g Na,CO,. I25 ml H,O, and brornocresol green. HCI N HCI = ,wt NalCO,)/
X9 111136% HCI per (ml x 0.05299)
liter H,O
0.1 N I, 0 2 g As20q, 20 ml I .O N NaOH, gently heat untd As,O, diawlves, Colorless-blue N I2 = (wr A\?031
12.7 g ll. 24.0 g KI cool, add phenolphthalein. I.0 N HCI added from pink to colorless. (ml X 11.03946)
per liter H,O 100 ml H1O. I ml cont. HCl. 2 2 hicarhonate added slowly, and
starch wlutmn.
0.01 N Hg(NO& 7.5 g KCI diswlwxi in Hz0 and ddutrd to I.000 ml m a volumetric H@0,)2 N Hg(NO,), = (wt KCI
I.083 g HpO. 5 ml f&k. Pipette 2.ml sample, add 100 ml H,O, and I5 ml 20% x ml r~Inplc)i(ml
50% HNO, per liter trichlonxlcetic actd. H_s(NO),)~ X 74.56)
HJI
0.1 N KI-KIO, In SWml flask add 0.20 g Sn. I00 ml cone HCI, 2 drop\ SbCI, KI-KID, Colorless-blue N KI-KIO, = (wt
3.6 g KIO,. I.0 g wlution. let stand at room temperature 1111diwTlved. Add I80 ml Sll)/(rnl x 0.05Y34S)
NaOH, IO.0 g KI per H,O, j-in folded “U-shaped nickel \tr~p. and 5.0 g reduced iron
hter Hz0 powder Slopper lla\k wth rubber wpper fitted with ‘/l-in. glass
tuhc ~mtnrrvxl into a aaturntcd NaHCO, solutmn. Heat wlution on
hot-plate to hod tar 20 mmute\ and then place in cooling tank and
allow to cool to 1’oom tcmprnlture. Make sure gin\\ outlet tube is
~mrmrwd III the NaHCO,. Remwe stopper and add rtarch wlution.
Table IV. Standsrdizatiun d Ybndrrd Solutions (cum.)

Culculariom (ml, N.
M-titmt; wt-sample
.s0frd0R Titrant Color Change in grams)

0.1 N KMnO, Heat KMnO, solution to near boding fu 30 minutes and let stand KMnO, Colorless-pink NKMnO,=
3.2 g KMnO, per liter overnight. Filter through a aintcrcd glass crucible. Then, to wt Na,C,O,)/
Hz0 standardize: add 0.2 g IVa,C,O,, 200 ml H,O, 30 ml 20% H,SO,, (ml X 0.0670)
beat fo 185-195’F.
0.1 N KSCN 0.3 I: AS, 15 ml 50% HNO,, 100 ml l&O, and FAS. KSCN Colorless-red N KSCN = (wt Ag)/
9.7 g KSCN per liter (ml X 0.10787)
W
0.1 AsNO, 0.2 t: NaCI, 125 ml H,O, sod K,CrO,. AiWx Yellow-red N AgNO, = (wt N&l)/
17.0 I: AgNO, per (ml X 0.05845)
liter HI0
0.1 N NaOH 0.5 g potassium hydrogen phthslate (KHC,H,O,j, 125 ml H,O, and NaOH Colorless-pink N NaOH =
4.0 g NaOH per liter phenolphthalein. W ~WW,)/
H,O (ml x 0.20422)
I .O N NaOH 4.0 g potawum hydrogen phtbalate (KHC,H,O,), I25 ml H,O, and NaOH Colorless-pink N NaOH =
4U.U g NaOH per liter phenolphthalein indicator. (wt KHC,H,O,)/
I&O (ml X 0.20122)
0.1 N Na,S,O., Add 0.1 g N&O., to N&O, solutton and let stand for 24 hours. Blue-colorless N N&O, = (wt
25.0 g N+S,O,+H, To standardiw add 0.12 g KIO,, 2 g KI, 25 ml HZO, and 8 ml KIO,)/(ml x 0.03567)
0 per liter Ii,0 10% HCI. Titrate to light qellow with N+S20, and add 2 ml starch
solution.
0. I N Th(NO,), 5.0 g NaF diswlvcd in H,O and Jduted to 1,UUU ml in a volumetric mNo3), Yellow-pink N = (WI NaF per
14.0 g tlask. Pipette l&ml sample, add 100 ml H,O. alizarin indicator, 2% liter)/(ml X 4.1998)
l’h(NO&,4HL0 per HNU,. dnrpwisc from pink to yelluw, and 3 ml fluoride buffer.
liter H,O
Table V. Indicators for Analyses
I .O g sodium alirarm sulfonate. I .nnO ml HzO.
0.4 g bromocresol green, 1,000 ml H,O, 0 5 ml I .O N NaOH.
0.4 8 bromocresnl purple, I.000 ml HzO. I .O ml I .O N NaOH.
2.0 s Eriochrome Black T, I98 ~0NaCI.
5.0 g Eriochrome Black T, 150 ml methanol. 100 ml trlethanolamlne.
SO p ferrous ammoGum wlfntc, 950 ml HLO. In ml cwt. HNO,.
20 g KJrO,. 9X0 ml H,O.
1.O s methyl orange (sodium \altL I.000 ml H,O.
2.0 g murexide. 198 g NaCI.
I .O g peroxyacetal nitrate. I.000 ml methanol.
I.0 g phenolphthalein. 500 ml cthsnol. 500 ml HzO.
IO.0 g ?tarch. 1.000 ml hot H,O, 0.5 ml formaldehyde.
IO0 ml sulfa oran,q. IO g NaCN. 845 ml H>O.

40 g nmmon~um oxalate, 960 ml HzO.

IO s dimethylglyoxime. I.000 ml ethanol.
01solve 40 g monochloroacetic aad in 400 ml Hz0 and divide the
solutmn m two equal parts. Add phenolphthalein to one pal-t alld
titrate with I .O N NaOH f~rwn coIorlew to pink Mix both parts
and add HZ0 to 1,000 ml.
100 g KF dirsolved in 1,000 ml HzO. Neutralize to pH 7.0 with
I .O N NaOH.
IO0 g NaCN, 900 ml H,O.
I35 g Na,SO,, 950 ml &O
3SO ml cont. NH,OH, S4 g NH,CI, 625 ml H20.
I00 ml cont. HCI. 250 ml cont. HC,H,O,. 200 ml ethanol.
4.50 ml H,O.
200 g Kochelle wits, X00 ml H?O.
2.0 g SbCI,. 100 ml 50% HCI.
IO s AgNO,, 95 ml H,O.
I00 g sodium sulfite, 950 ml H,O. Ad,ju\t to pH 9.0 with I.0 N
NaOH or I.0 N HCI. Solution ha\ a I-week shelf hfe.
IS0 g tartaric acid, 950 ml H20.

Table VII. Properties of Reagent Grade Acids

ACId F,mmrlu Wf ‘2 Specific Gruvirv (60°F) Porrr~dr/Gall,m

Acetic HC,H,OZ 99 .o I .oso X.76

Fluoboric HBF, 48.0 I.365 I I .3X
FllWllC HCHO, 98.0 I .220 in.17
Hydrobromlc HBI 48.0 1.490 Il.43
Hydrochloric HCI 36.0 I.181 9.87
Hydrofluoric HF 70.0 I .256 IO.48
Nitric HNO, 70.0 I.420 1 I XJ
Phosphoric HJ-3, 85.0 I.690 13.09
Sulfuric H,SO, 93.0 I.835 IS.30

536
Table VIII. Test Methods for Electroplating Solutions

Erusc
CuCN (Method I) 2 ml IS ml cont. HNO,. heat to blue color, 0.1 M EDTA Purple-green CuCN (&gal) = 2.985 X M X [2 X
IO0 ml H,O,” cont. NH,OH to deep CuCN ml - 0.8 X Zn(CN), ml]
blue, heat to 140°F. and add PAN.

CuCN (Method 11) 2 ml 100 ml HzO. 15 ml cow. HNO,, heat to 0.1 N N&O, Blue-colorless CuCN (or/gal) = ml X 5.971 X N
blue color and disappearance of brown
fumes, NH,OH to deep blue. acetic acid
to light blue, 5 g KI. Titrate with
N&O, to pale yellow. add 5 ml starch
solution, continue titrating to colorless.

Zn(CN), 5 ml IO0 ml H,O, 10 ml pH IO buffer, EBT 0. I M EDTA Red-blue Zn(CN), (o~igal) = ml X 3.131 X M
powder, and I5 ml 10% formaldehyde.

NaCN or 5 ml 100 ml H,O and 10 ml IO% KI. 0.1 N AgNO, Clear-turbid NaCN (oz/gal) = ml X 2.614 X N
KCN KCN to&gal) = ml X 3.473 X N

NaOH or 5 ml 25 ml Hz0 and 5 ml culfo-orange. 1.0 N HCI Orange-yellow NaOH (o&al) = ml X 1.067 X N
KOH KOH (or/gal) = ml X 1.496 X N

Na,CO, or IO ml 100 ml hot H,O, 35 ml 10% Ba(NO&. I .O N HCl Orange-pmk Na,CO, (or/gal) = ml X 0.707 X N
allow to settle. filter. wash filter twce K&O, (o71gz.l) = ml X 0.921 X N
KG’,
with hot H,O, transfer filter paper and
precipitate to a beaker. add lo0 ml H,O,
and methyl orange.
Tuble VW. Test Metl~u& fur Elwtruplating Sulutiuns ~w~r.)

Heagenrs
Burt1 Surnple Sire (To be died in u&r listed) Titrunt Color Change Calculations (ml. iV. M-tirrunt)

KNaC,H,0,.4H20 5 ml 25 ml 20% H,SO,. filter, wash tIa%k and 0.1 N KMnO, Colorless-pink KNaC,H,0,,~4HaO (ozlgal) =
filter paper twice each with H,O, and ml X 1.250 X N
boil the collected fittrate 5 minutes,
Btwn~e
Cu (Method I) 2 ml 15 ml cont. HNOs, heat to blue color, 0. I M EDTA Purple-green Cu (oz/gal) = ml X 4.236 X M
lo0 ml H,O, cont. NH,OH to deep blue.
heat to IllO’F and dd PAN.

Cu (Method II) 2 ml 100 ml H,O. I5 ml corm. HNO,, heat to 0. I N Na,S?O, Blue-colorless Cu (ozlgal) = ml X 4.236 X N
blue color and disappearance of brown
fumes, NH,OH to deep blue, acetic acid
to light blue, 5 g KI. Titrate with
Na,S,O, to pale yellow, add 5 ml starch
solution, continue titrating to colorless.

Sn 5 ml 100 ml H20. 50 ml cont. HCI, 3.0 g iron 0.1 N KI-KIO, Clear-blue Sn (or&I) = ml X I.5113 X N
powder in 500.ml tlask. Stopper flask
with stopper litted with a glass tube
Immersed in a beaker filled with
saturated bicarbonate solution. Heat
gently till iron dissolves. Cool to room
temperature, making sure outlet tube is
immersed in bicarbonate solution. Add
10 ml stamh solution and bicarbonate
during titration.

NaCN or 5 ml IO0 ml Ha0 and IO ml IOKI. 0.1 N AgNO, Clear-turbid NaCN (&gal) = ml X 2.614 X N
KCN KCN (or/gal) = ml x 3.473 x N

NaOH or 5 ml 25 ml Hz0 and S ml rullo-orange. I .o N tic1 Orange-yellow NaOH (otigal) = ml x I.067 x N

KOH KOH (oz./gal) = ml X I.496 X N
Table VIII. Test Methods for Electroplating Solutions (cont.)

Bath Sump/e Six!

NaJO, or IO ml 100 ml hot HzO, 35 ml 10% Ba(NO&, 1.0 N HCI Orange-pmk NaJO, (adgal) = ml x 0.707 x N
K&O, allow to settle, filter, wash filter twice KLCO, (o&d) = ml x 0.921 X N
with hot H,O, transfer filter paper and
precipitate to a beaker, add 100 ml H20
and methyl orange.

KNaC,H,0,.4HI0 5 ml 25 ml 20% H,SO,, filter, wash flask and 0.1 N KMnO, Colorless-pink KNaC,H,0,.4H20 (or/gal) =
filter paper &ice each with H,O. and ml X 1.250 X N
boil the collected filtrate 5 minutes.
Cudmium Cymide
Cd 2 ml 100 ml H,O, 10 ml pH IO buffer, EBT 0.1 M EDTA Red-blue Cd (or/gal) = ml x 7.493 X M
powder, and IS ml 10% formaldehyde.

Total and 5 ml 100 ml HzO, 15 ml cow. NH,OH, and 0.1 N AgNO, Clear-turbid Total NaCN (ozlgal) = ml X 2.613 X N
Free NaCN IO ml 10% KI. Free NaCN (or/gal) =
Total NaCN - 1.744 X Cd
NaOH s ml 25 ml HZ0 and 5 ml sulfa-orange. I .O N HCI Orange-yellow NaOH (ozlgal) = ml X I.067 X N

NnJO, 10 ml IO0 ml hot HZO, 3.5 ml 10% Ba(NO&, I .O N HCI Orange-pink NaJO, (w/gal) = ml X 0.707 X N
allow to settle, filter, wash filter twce
with hot HzO, transfer filter paper and
precipitate to a beaker, add 100 ml H,O
and methyl orange.

100 ml H20, IO ml pH IO huffcr, EBT 0.1 M EDTA Red-blue Cd (w/gal) = ml x 7.493 X M

powder, and 15 ml 10% formaldehyde.
3
Table VIII. Test Methods for Electroplating Solutions (umr.)

25 ml 100 ml H,O. 100 ml rcducmg solution. SO, (dpall = (weight tn :rnms of

hoi1 30 minutes, remove from heat, add precipitate) x 2.195
SO ml 10% Ba(NO?),, 100 ml hot H,O.
Allow aolutmn to wnd for 311 hours,
heat solution to bolhng. Filter in tared
Gooch crucible, wash preapitate wth hot
H:O, dry in oven at 110°C. cool ,n
dewcatnr and wafh.

5 ml 100 ml H,O, I.0 N NaOH to pH 7.5. 0. I N Th(NO,), Yellow-pink F (o-r&d) = ml X 0.507 X N

using a pH meter previously standardtzed
to pH 7.0. Add 10%’ AgNO, solution
until the dlsappeartwce of the yrllnw
color after scttlinf of the precipitate,
flltcr, wash prccipute, swe filtrate. Add
Alirarm Indicator. 2% HNO, till color of
wlution changes from pink to yellow.
Add 3 ml tluorldc huffer.

Co/~/w Cwmide
CuCN (Method I) 2 ml IS ml cont. HNO,. heat to blue C&II-. 0.1 M EDTA PWple-prWl CuCN (o&d) = ml X 5.971 X M
100 ~ml H>O, cont. NH,OH to deep hluc.
hut to 140°F. and add PAN.

CuCN (Method II) 2 ml 100 ml HZO. IS ml cow. HNO,. heat to 0.1 N Na,S,O, Blue-colorless CuCN (w/gal) = ml X 5.971 X N
blue color and disappearance of brown
fumes, NH,OH to deep blue. acetic actd
to light blue, 5 g KI. Titrate wth
Na,S,O, to pale yellow. add 5 ml starch
wlution, continue titrating to colorleu.
E
N Table VIII. Test Methods for Electroplating Solutions (wn~.)

NaCN or 5 ml I00 ml H,O and IO ml IO% KI. 0.1 N AgNO, Clear-tttrbtd NCN (w/gal) = ml X 2.614 X N
KCN KCN (w/gal) = ml x 3.473 X N

NaOH 01 5 ml 25 ml Hz0 and 5 ml aulfo-orange. I .O N HCI Orange-yellow NaOH (ozigall = ml x I.067 x N

KOH KOH (ozifal) = ml X 1.496 X N

IO ml I00 ml hot H,O, 35 ml 10% Ba(NO,)>. I .O N HCI Orange-pink Na,CO, (~&VI) = ml X 0.707 X N
~110~ tu settle. filter, wash filter twice KJO,. etc
with hot HZO. transfer filter paper and K,CO, (o//gal) = ml x ll.Y21 X N
precipitate to a beaker, add 100 ml H,O,
and methyl orange.

KNnC,H,0;4H20 5 ml 2S ml 20% H2S0,, filter, wash flask and 0.1 N KMnO, Colorless-pink KNaC,H,O,.4H,O (w/gal) =
filter paper twice each with HzO. and ml x I.250 X N
bowl the collected filtrate 5 minutes.

2 ml 100 ml H,O, cow. NH,OH to deep blue, 0.1 M EDTA Purple-green Cu (o&l) = ml X 4.236 X M
heat to 140-F. and add PAN CUBF,), i&gal) = Cu X 3.73

Cu (Method II) 2 ml IO0 ml HLO, NH,OH to deep blue, 0. I N Na2S20, Blue-colorlas Cu (ozlgal) = ml x 4 2% X N
acctw acid to light blue, 5 g KI. Titrate
with N&O, to pale yellow, add 5 ml
starch wlution, continue titrating to
WlWl%S.

IO ml IO0 ml Hz0 and methyl orange. I .O N NaOH Red-preen lOOr/, HBF, (oz/.&) = ml X I.171 X N

2 ml 100 ml H,O cont. NH,OH to deep blue. 0.1 M EDTA Cu (or/gal) = ml X 4.2X1 X M
heat to 140°F and add PAN.
 Table VIII. Test Methods for Electroplating Solutions (conr.)

Reagents
Bath Sample Size (To he added in order listed) TiVfWU Color Change Calculations (ml. N. M-titrant)

Cu (Method II) 2 ml 100 ml H,O, NH,OH to deep blue, ace- 0.1 N Na,S>O, Blue-colorless Cu (oz/gal) = ml X 4.236 X N
tic acid to light blue, 5 g KI. Titrate with
Na&O, to pale yellow, add 5 ml starch
solution, continue titrating to colorless.
Total P,O, 5 ml 100 ml H,O, 1.0 N HCl dropwise to pH I .O N NaOH Total P,O, (oz/gal) =
3.8 (use pH meter standardized at pH ml X 2.32 X N + Cu X 1.37
4.0), back-titrate with 1.0 N NaOH if pH Ratio = [Total P,O, (oz/gal)llCu
3.8 is overshot, stir 5 minutes and make Codgal)
sure pH is 3.6-3.8, add 50 ml 20%
ZnSO, (adjusted to pH 3.8) and stir IO
minutes. Titrate slowly with stining
using 1.O N NaOH to pH 3.8 (note these
ml NaOH used for calculation).

10 ml 200 ml HzO, boiling chips, 50 ml 20% 0.1 N HCI Yellow-red 29% NH, (oz/gal) = ml x 0.80 x N
NaOH III Kjeldabl flask. Attach flask to
the distillation apparatus with the
collection tube from the condenser
immersed m a beaker containing 100 ml
saturated H,BO? solution. Boil flask and
diqtdl over 100 ml. Remove beaker and
add methyl orange.

Copper sulfate
Cu (Method I) 2 ml 100 ml HzO, cont. NH,OH to deep blue, 0.1 M EDTA Purple-green Cu (&gal) = ml X 4.236 X M
heat to 140°F. and add PAN. CuS0,.5Hz0 (oz/gal) = Cu X 3.93

Cu (Method II) 2 ml 100 ml H,O. NH,OH to deep blue, 0.1 N N&O, BIIECOlOTkSS Cu (w/gal) = ml X 4.236 X N
acetic acid to light blue, 5 g KJ. Titrate
with Na,S,O, to pale yellow, add 5 ml
starch solution, continue titrating to
colorless.
W
 r

-2
545
t
Table VIII. Test Methods for Electroplating Solutions (mu.)

Titranr Color Chun@? Calculutions (m/, N, M-ritmnr)

-
Ni 2 ml 100 ml H,O, IO ml cow NH,OH, and 0.1 M EDTA Orange-purple Ni (w/gal) = (ml EDTA for Ni - ml
murexide powder. EDTA for Zn) X 3.914 X M

NaSCN 10 ml 100 ml H,O, 15 ml 20% H$O,, and 0.1 N AgNO, Red-colorless NaSCN (oz./gal) = ml X I.081 X N
FAS indicator.

Nickel Fluobnmfr
Ni 2 ml 100 ml HzO, IO ml cow. NH,OH, and 0.1 M EDTA Orange-purple Ni (or/gal) = ml X 3.914 X M
murexide powder.

HP% IO ml 25 ml H20, 5.0 g mannitol, and I .O N NaOH Green-purple H,BO, (“z/gal) = ml x 0.824 x N
bromocresol purple.

Nickel Strike
Ni 2 ml 100 ml H,O, 20 ml cont. NH,OH, and 0.1 M EDTA Orange-purple Ni (o&gal) = ml X 3.914 X M
murexide powder.

HCI 10 ml IO ml HZ0 and methyl orange. 1.O N NaOH Red-yellow/green 36% HCI (tl oz./gal) = ml X I.1 IS x N

Nickel Sulfamute
Ni 2 ml 100 ml HzO, 20 ml cont. NH,OH, and 0.1 M EDTA Orange-purple NI (oz/pal) = ml x 3.914 x M
murexide powder.

NiBrz 5 ml 100 ml H,O and K,CrO,. 0.1 N AgNO, Yellow/green-red NiBr, (oz1gal) = ml X 2.914 X N

NiC12.6H,0 20 ml 100 ml HZ0 and KZCrO,. 0. I N AgNO, Yellow/gretwed NiCl,.6Hz0 (ozlgal) = ml x 0.792 x N

WC’, IO ml 25 ml HZO. 5.0 g mannitol, and I .O N NaOH Green-purple H,BO, (oz./gal) = ml X 0.824 X N
hromocresol purple.
 c

548
 Table VIII. Test Methods for Electroplating Solutions (cont.)

Reagents
Ruth SamDIe Six7 (To be added in order listed) Tirrunt Color Channe Calculutimr (ml. N, M-titrunt)

Palladium
Pd IO ml IO ml cont. HNO,, heat untd syrupy, IO Pd (g/L) = (weight in grams of
ml cont. HNO,, heat to onset of boiling. precipitate) X 3 I .67
Add 250 ml H,O, cool, slowly add 40
ml dimethylglyoxime solution, allow
solution to stand at least 2 hours, filter
through No. 3 porosity tared crucible,
wash precipitate with H20. Dry in oven
at 1IO’C, cool m desiccator, and weigh.
Platinum
Pl IO ml 10 ml cont. HCI, heat until syrupy, 100 Pt (g/L) = (wetght in grams of
ml H,O, 5 g sodium acetate, 1 ml cont. precipitate) X 100.0
formic acid, heat at l40’F for 5 hours,
filter, wash precipitate with hot H,O.
Place filter paper and Pt precipitate in
tared porcelain crucible, dry slowly with
Bunsen burner, char filter paper, dry Pt
precipitate at high temperature for 30
mmutes. Cool in desiccator and weigh.
Rhodium
Rh 25 ml 2 g Mg turnings, cont. HCI dropwise. Rh (g/L) = (weight in grams of
When all Mg dissolves, add 0.5 g Mg precipitate) X 40.0
tummgs and HCI dropwise to ensure
complete precipitation of Rh. Filter
solution in tared Gooch crucible
containing fiberglass filter paper, wash
precipitate with hot HzO, dry in oven at
I IO’C, cool in desiccator and weigh.

WO, or IO ml 100 ml H,O and methyl orange. I .O N NaOH Red-yellow/green 100% H,SO, (g/L) = ml X 4.904 X N
HP% 100% H,PO, (g/L) = ml X 9.800 X N
E!
W
Table VIII. Test Methods for Electroplating Solutions (cont.)

Keu,Lynrs-
Buth Smple six (To be added bt order- listed) Titrunt Color Cllun,~r ~‘dulutions (ml, N, M-trtmt)

SIld+ 2 1111 In 500-ml flask add sample, III0 ml 0.1 N KI-KIO, CokIrleSS-blUe SnJ+ (o/gal) = ml X 3.Y.56 X N -
cow. HCl, 2 drops ShCI, solotlon. Add S”L+
IX0 ml H>O. Sin. folded ‘V-shaped
nickel strip and 5.0 g reduced non
powder. Stopper flask with ruhhet
<topper fitted wth %-in. &is\ tube
lmmeraed into a saturated NaHCO,
wlution. Heat solwon on hot plate to
hoi1 for 20 minutes and then place ix
cooling tank and allow to cool to room
temperature. Make WC glass outlet tuhc
IS umnersed in the NRUCO,. Remove
stopper and add starch aolutirn.

HBF, IO ml 100 ml HLO and methyl orange. I.0 N NaOH Clear-turbid 100% HBF, (or/gal) = ml X I.171 X N

Free H,BO, IO ml 100 ml H20, IO ml Na2S0, solution. I .tl N NaOH H,BO, (or/gal) = ml X 0.824 X N
Titrate to pH 7.0, using a pH meter
previously standardized to pH 7.0. Add S
g manmtol, titrate from pH 7.0 to pH X.0
(ml NaOH required for thin step we used
for the calculation).
Tin Srannate
KZSn0,.3HZ0 5 ml 100 ml H,O. 50 ml cont. HCI. 3.0 g iroll 0. I N KI-KIO, COlOibS-blue K,Sn0,.3HI0 (cr//g;d) = “~1 X 3.986 X
powder in SW-ml tlask. Sropper llask N
NazS”0,.3Hz0 with stopper fitted with a glass tube Na,Sn0,.3H10 Wgall =
immcrscd in a beaker filled with ml x 3.5% x N
saturated bicarbonate solution. Heat
gently till iron dissolves. Cool IO ro+)ln
tempcratturc, making sure outlet tuhr is
immersed in bicarbonate solution. Add
10 ml starch solution and bicarbonate
during titration.

KOH 5 ml 25 ml H,O and S ml sulfo-orange 1.0 N HCI Orange-yellow KOH (ox&l) = “11 X I.196 X N
NaOH NuOH (o/&al) =- “11 X 1.067 X N

Tin Sulfute
snso, 5 ml 100 ml H20, 25 ml 50% HCI, IO ml 0.1 N KI-KIO., Colorless-blue SnSO, (oz./gel) r ml X ‘.X63 X N
starch solution, add bicarbonate during S”” (oz./gal) = SnSO, x 0.5.53
titration.

S”4’ 2 ml In SW-ml fla.k add sample. 100 ml 0.1 N KI-KIO, Colorless-blue Sn4+ (oIlgal) =
cont. HCI, 2 drops SbCI, solution. Add ml x 3.956 X N .- Sn”
180 ml l-1,0. 5-i”. folded “U’-shaped
nickel strip and 5.0 g reduced imn
powder. Stopper flask with rubber
stopper fitted with %-in. glass tube
immersed into a saturated NaHCO,
solution. Heat solution on hot-plate to
boil for 20 minutes and then place in
cooling tank and allow IO cool to room
temperature. Make sure glass outlet tube
is immersed in the NaHCO,. Krmove
stopper and add starch solution.
Table VIII. Test Methods for Electroplating Solutions (wm.J

HZSO, 100 ml H,O, 25 ml ammonium oxalate I .O N NaOH Red- 100% H:SO, (or/gal) = ml X 0.654
solution, and methyl orange. oranpc/yellow % v H,SO, = ml X 0.279 X N

100 ml H,O, 25 ml SO6 HCI, IO ml starch 0.1 N KI-KIO, Colorle\\-blue St? (w&al) = ml X 3.956 x N
sufut~on, add burbonate during tenon

St?+ 2 ml In St&ml flask add sample, I00 ml 0.1 N KI-KIO, Colorless-blue Sn” (o&al) =
cow. HCI, 2 drops SbCI, soIut\w. Add ml x 7.956 X N - Sn“
180 ml H,O, 5-in. folded “Wshaped
nickel strip and 5.0 g reduced ~rnn
powder. Stopper flask with rubber
stopper fltted wth %-in. glass tube
Immened into ;t uturated NaHCO,
wlution. Heat solution on hot-plate to
boil I’or 20 minutes and then place m
cooling tank and allow to cool to worn
temperature. Make cure gla\\ outlet tube
is immersed in the NaHCO,. Remwe
stopper and add \tarch \oI~t~m~.

Ph 2 ml 5 ml cow. HNO,, heat till sympy. cool 0. I M ElIT.4 Red-blue Pb torigal) = 1111X 13.X13 X M
and add: 25 ml Rochelle solutmn, IS ml
cont. NH,OH, 15 ml 10% NaCN and
EBT solution.

HBF, IO ml 100 ml H,O. I .O N NaOH Clcsr-tul-hid 1004 HBF, (ozigal) = ml X I.171 X N

 E

554
555
 The Technology of
Anodizing Aluminum,
Third Edition
by A. II? Brace
410 pages $210.00
NE WEDITION This valuable
book has been completely re-
edited and considers signifi-
cant new developments in
anodizing technology. The
expanded volume will satisfy
the anodizer who requires
more detailed technology.
After an introduction, the
reader is presented with practi-
cal application of the new
technology, and the nature of
the industry with capital
investment appraisal, budget-
ing, and cost control. An
excellent summary of anodiz-
ing technologies in clear lan-
guage encompassing the advice
of exierienced technicians.

Send Orders to:

METAL FINISHING
660 White Plains Rd.
Tarrytown, NY 10591-5153

For faster service,

call (914) 333-2578
or FAX your order
to (914) 333-2570
All book orders must be prepaid. Please
include $5.00 shipping and handling for
delivery of each book via UPS in the U.S..
$10.00 for each book shipped express tc
Canada; and $20.00 for each book shipped
express to all other countries.
557
is
a3 Table X. Test Methods for Anodizing Solutions

IO ml IO ml sample intc 500 ml volumetric. 0.1 N Na,S,O, BlU+WM~\~ 00, (ozlgal) = ml x 22.219 X N
of stock Pipette IO ml of stock, add 100 ml
H,O,” 2 g ammonium hifluoride, 15 ml
cont. HCI, IS ml IO% Kl, and starch
solution.

Free 00, 25 ml l(X) ml H,O. Titrate to pH 3.05, using a I ..I N NaOH Colorless-pink Free 00, (or/gal) = ml X 0.533 X N
pH meter prevtously standardized to pH
4.0.
Sdjiirric
Total H,SO, s ml 100 ml H20 and phenolphthalein. I .O N NaOH Colorlew-pink Total H,SO, (c&gal) = ml X 1.308 X N
Free H,SO, 5 ml 100 ml HIO. IO ml KF solution, and I .O N NaOH Colorlewpink Free H,SO, (oz&al) = ml X 1.308 X N
phrnolphthalrin.

Al Al (or/gal) = (ml NaOH for Total

H$O, - ml NaOH for free H,SO,)
X 0.240 X N
Table XI. Test Methods for Acid Dips and Electropolishing Solutions

HW,O, 10 ml 100 ml HZO” and phenolphthalein. I .O N NaOH Colorless-pmk ‘70 wt HC,H,O, (100%) = (ml X 0.6005
X N)/s.g. solution
“&“&“,~ IO ml 100 ml H20 and phenolphthalein. I .O N NaOH Colorless-pink o/c wt H 3C 6H i 0 7.H,O = (ml X 0.7005
(Citric acid) X N1h.g. wlutmn
HBF, IO ml 100 ml H,O and melhyl orange. I .O N NaOH Red-yellow/green % wt HBF, (100%) = (ml X 0.8781 X
N)/s.g. solution
HCI IO ml IO0 ml HLO and methyl orange. I .O N NaOH Red-yellow/green Q wt HCI (100%) = (ml X 0.3646 X
N)/s.g. solution
HF 2s 100 ml Hz0 and phenolphthalein. I .O N NaOH Colorlewpink ‘% wt HF (100%) = (ml x 2.001 x
(Note: use plastic lahware.) N)/wt
HNO, IO ml 100 ml HZ0 and methyl orange. 1.O N NaOH Red-yellow/green s/c wt HNO, (100%) = (ml ‘* 0.6301 X
N)/s.g. solution
W’O, IO ml 100 ml Hz0 and methyl orange. I .O N NaOH Red-yellow/green ‘h wt H,PO, (100%) = (ml Y 0.9800 x
N&g. solution
H2S0, IO ml IO0 ml H,O and methyl orange I .O N NaOH Red-ycllowlgreen %, wt HISO, (100%) = (ml X 0.4904 X
N)/a.g. solution
HNO, + HF IO ml 100 ml HZ0 and methyl orange. I .O N NaOH Red-yellow/green A ml
I ml IO0 ml H,O. Alirarin, I .O N NaOH to 0. I N Th(NO,), Yellow-pink B ml
pink. 2% HNO, dropwisc born pink to 5’4 wt HNO, (100%) = [(A ml X N ~
yellow, 3 ml fluoride buffer. IO X B ml X N) X 0.6301]/~. wlution
% wt HF (1001) = (B ml X 20.006 X
N)/s.g. solution

H3P0, + H$O, IO ml 100 ml H,O and methyl orange. I .O N NaOH Ked-yellow/green A ml

Add phenolphthalein to the solution I .O N NaOH Purple-red B ml
above.
D/ wt H,SO, (100%) = ((A ml ~ B ml)
X 0.4904 X N]/s.g. solution
B wt H,PO, (100%) = (B ml x
0.9800 X N)/s.g. solution
H$O, + IO ml I00 ml H,O and methyl orange. I .O N NaOH Red-yellow/green % wt H$O, (100%) = (ml x 0.4904 x
N)ls.g. solution
 IX

560
NQO 25 ml IOU ml HLO” and methyl orange I .O N HCI Yellow-orangcircd Na,O (w&al) = ml X 0.165 X N
Na2C0, + NaOH IO ml IO0 ml H,O and sulfa orange. I .O N HCI Orange-yellow B ml
IO ml 100 ml Hz0 and methyl orange. I .O N HCI Yellow-orange/red A ml
Na,CO, (n/gal) = (A ml ~ B ml)X
0.707 X N
NaOH (or/gal) = B ml X 0.533 X N
NaOH + NaCN 10 ml 100 ml H,O and sulfa orange. I .O N HCI Orange-yellow NaOH (w/gal) : ml X 0.533 X N
NaOH
NaCN IO ml 100 ml H,O and IO ml IO% Kl. 0.1 N AgNO, Clear-turbid NaCN (@cd) = ml X I.307 X N
NaZCO, + NaCN Ill ml III0 ml H,O and methyl orange. I .O N HCI Yellow-orange/red A ml
IO ml 100 ml H,O and IO ml 10% KI. 0.1 N AgNO, Clear-turbid B ml
NaCN (wignl) = B ml X I.307 X N
Na2C01 (rv/gal) = (A ml X N - B ml
X N) X 0.707
NaJO, + IO ml IS0 ml H,O and methyl orange. I .U N HCI Yellow-orange/red A ml
Na,PO,
Boil above solulron 5 minutes, cool. I .O N NaOH B ml
and add phenolphthalein.
Na,PO, (n/gal) = B ml X 2. I X6X N
Na,CO, (w/gal) = (A ml X N ~ 2 X B
ml X N) X 0.707
Na,PO, + NaCN + IO ml 150 ml H,O and methyl orange I .O N HCI Yclloworangc/red A ml
NazSi0,.5Hz0
Boil ahove solution 5 minutes, cool. I .U N NaOH Colorles-pink B ml
and add phenolphthalein.
10 ml IOU ml Hz0 and IO ml 10% KI. (1.1 N AgNO, Clear-turbid c 1111
Na,PO, (w/gal) = B ml X 2.186X N
NaCN (u/gal) = C ml X 1.307 X N
NazSiO,.SHZO (w/g~l) = (A ml X N ~
2 X B ml X N C ml X N) X 1.414
562
Table XIII. Alternate Method for Chromic Acid
Drjirees BuumP O~/@lI-cro ( De~wes BuuntP od#lI-Cro~,

I .so 2.1 19.00 29.0

2.00 2.8 19.50 29.8
2.50 3.4 20.00 30.6
3.00 4.1 20.50 31.5
3.50 4.8 21.00 32.4
4.00 5.5 2 I so 33.3
4.50 6.2 22.00 34.2
5.00 6.8 22.50 3.5.1
5.50 7.5 23.00 36.0
6.00 8.2 23.50 37.1
6.50 8.9 24.00 3x.2
7.00 9.7 24.50 39. I
7.50 10.4 2.5.00 40.0
8.00 I I.1 25.50 40.9
X.50 Il.9 26.00 41.9
9.00 12.6 26.50 42.9
9.50 13.4 27.00 44.0
I 0.00 14.2 27.X) 4.5.o
IO.50 IS.0 28.00 46.0
II.00 15.x 28.50 47.1
I I.50 16.5 29.00 48.2
12.00 17.3 29.X) 49.2
12.X) I x.2 30.00 SO.2
I3.00 19.1 30.50 51.5
13.50 19.8 31.00 52.7
14.00 20.4 31.50 54.0
14.50 21.2 32.00 55.2
IS.00 22.0 32.50 56.3
IS.50 22.9 33.00 57-S
16.00 23.7 33.50 58.7
16.50 24.5 34.00 60.0
17.00 2.5.4 34.50 61.2
17.50 26.3 35 .oo 62.3
I x.00 27.2 35.50 63.5
IX.50 28. I 36.00 64.X

Pmxdure: I. Cool the solution to room temperature after tating.

2. Dctemine the demity 01 the soluuon with a F&m& hydrometer.
3. Read the or/gal OSchrrmmw aud (CrOj) corre~pondm~ to thl\ dcmily

Chromium Plating
by R. Weiner and A. W&r&y 239 pages $115.00

A thorough and well-written book on both decorative and engineering (hard) chromium plat-
ing, it will be of interest to anyone engaged in production chromium plating and also to stu-
dents, researchers, and design engineers. Anyone contemplating the installation of chromium
plating facilities will find it of special value.

Send Orders to: METAL FINISHING., 660 White Plains Rd., Tarrytown, NY 10591-5153
For faster service, call (914) 333-2578 or FAX your order to (914) 333-2570
All book orders rnasf be prepaid. Please include $5.00 shipping md handling for delivery of each book via UPS to
addresses in rhe U S., 1110.00for each book shipped express to Cmada; md $20.00 for each book shipped express to
all other countries.

563
Table XIV. Alternate Method for Copper Sulfate

1.5 2.x 14.5 24.7

2.0 3.5 IS.0 25.7
2.5 4.3 15.5 26.8
3.0 5.1 16.0 27.8
3.5 5.9 16.5 2x.x
4.0 6.1 17.0 29.x
4.5 7.4 17.5 30.8
5.0 x.2 18.0 31.x
5.5 9.0 IX.5 32.X
6.0 9.x 19.0 33.x
6.5 10.6 19.5 34.9
7.0 I I.5 20.0 35.9
12.3 20.5 37.0
13.1 21.0 38.1
13.9 21.5 39.2
14.8 22.0 40.4
15.7 22.5 41.6
16.6 23.0 42.x
17.5 23.5 43.9
18.3 24.0 IS.0
19.2 24.5 46. I
20.0 25.0 47.3
21.0 25.5 3x.5
21.9 26.0 49.7
22.9 26.5 51.0
23.X 27.0 52.3

Printed Circuits Handbook, Fourth Edition

by CF. Coombs, Jr. 914 pages $90.00
This how-to book is a must for the practioner’s technical shelves and is required reading
for anyone involved with the everyday PI-ohlrms arising in p rimed circuit manufacture.
All aspects of the fabrication process are considered.

Send Orders to: METAL FINISHING, 660 White Plains Rd., Tarrytown, NY 10591-5153
For faster srrwce, call (914) 333-2578 or FAX pour order to (914) 333-2570

564