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Specific transition ranges depend on the
The pH ranges shown are approximate.
indicator solvent chosen.
Reprinted by permission of the Hach Company
PERIODIC TABLE OF THE ELEMENTS
Metals
IA VIIA 0
1 Nonmetals 17 18
1 Metalloids 1 2
1 H IIA IIIA IVA VA VIA H He

1.008 2 13 14 15 16 1.008 4.0026
3 4 5 6 7 8 9 10
Li Be B C N O F Ne
Unless otherwise noted, all content on this page is © Cengage Learning.

2
6.941 9.0122 10.81 12.011 14.007 15.999 18.9984 20.1797
11 12 VIIIB 13 14 15 16 17 18
3 Na Mg IIIB IVB VB VIB VIIB IB IIB Al Si P S Cl Ar

22.9898 24.3050 3 4 5 6 7 8 9 10 11 12 26.9815 28.085 30.9738 32.06 35.453 39.948
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39.0983 40.078 44.9559 47.867 50.9415 51.9961 54.9380 55.845 58.9332 58.6934 63.546 65.38 69.723 72.63 74.9216 78.96 79.904 83.798
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.4678 87.62 88.9058 91.224 92.9064 95.96 (98) 101.07 102.9055 106.42 107.8682 112.411 114.818 118.710 121.760 127.60 126.9045 131.293
55 56 57 * 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
6 Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
132.9055 137.327 138.9055 178.49 180.9479 183.84 186.207 190.23 192.217 195.084 196.9666 200.59 204.38 207.2 208.9804 (209) (210) (222)
87 88 89 ** 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118
7 Fr Ra Ac Rf Db Sg Bh Hs Mt Ds Rg Cn Uut Fl Uup Lv Uus Uuo

(223) (226) (227) (265) (268) (271) (270) (277) (276) (281) (280) (285) (284) (289) (288) (293) (294) (294)
*Lanthanide Series
58 59 60 61 62 63 64 65 66 67 68 69 70 71
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
140.116 140.9076 144.242 (145) 150.36 151.964 157.25 158.9254 162.500 164.9303 167.259 168.9342 173.054 174.9668
Note: Atomic masses are 2009 ** Actinide Series
IUPAC values (up to four decimal 90 91 92 93 94 95 96 97 98 99 100 101 102 103
places). More accurate values for
some elements are given in the Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
table inside the back cover. 232.0381 231.0359 238.0289 (237) (244) (243) (247) (247) (251) (252) (257) (258) (259) (262)
International Atomic Masses
Atomic Atomic Atomic Atomic
Element Symbol Number Mass Element Symbol Number Mass
Actinium Ac 89 (227) Mendelevium Md 101 (258)
Aluminum Al 13 26.9815386 Mercury Hg 80 200.59
Americium Am 95 (243) Molybdenum Mo 42 95.96
Antimony Sb 51 121.760 Neodymium Nd 60 144.242
Argon Ar 18 39.948 Neon Ne 10 20.1797
Arsenic As 33 74.92160 Neptunium Np 93 (237)
Astatine At 85 (210) Nickel Ni 28 58.6934
Barium Ba 56 137.327 Niobium Nb 41 92.90638
Berkelium Bk 97 (247) Nitrogen N 7 14.007
Beryllium Be 4 9.012182 Nobelium No 102 (259)
Bismuth Bi 83 208.98040 Osmium Os 76 190.23
Bohrium Bh 107 (270) Oxygen O 8 15.999
Boron B 5 10.81 Palladium Pd 46 106.42
Bromine Br 35 79.904 Phosphorus P 15 30.973762
Cadmium Cd 48 112.411 Platinum Pt 78 195.084
Calcium Ca 20 40.078 Plutonium Pu 94 (244)
Californium Cf 98 (251) Polonium Po 84 (209)
Carbon C 6 12.011 Potassium K 19 39.0983
Cerium Ce 58 140.116 Praseodymium Pr 59 140.90765
Cesium Cs 55 132.90545 Promethium Pm 61 (145)
Chlorine Cl 17 35.45 Protactinium Pa 91 231.03588
Chromium Cr 24 51.9961 Radium Ra 88 (226)
Cobalt Co 27 58.933195 Radon Rn 86 (222)
Copernicium Cn 112 (285) Rhenium Re 75 186.207
Copper Cu 29 63.546 Rhodium Rh 45 102.90550
Curium Cm 96 (247) Roentgenium Rg 111 (280)
Darmstadtium Ds 110 (281) Rubidium Rb 37 85.4678
Dubnium Db 105 (268) Ruthenium Ru 44 101.07
Dysprosium Dy 66 162.500 Rutherfordium Rf 104 (265)
Einsteinium Es 99 (252) Samarium Sm 62 150.36
Erbium Er 68 167.259 Scandium Sc 21 44.955912
Europium Eu 63 151.964 Seaborgium Sg 106 (271)
Fermium Fm 100 (257) Selenium Se 34 78.96
Flerovium Fl 114 (289) Silicon Si 14 28.085
Fluorine F 9 18.9984032 Silver Ag 47 107.8682
Francium Fr 87 (223) Sodium Na 11 22.98976928
Gadolinium Gd 64 157.25 Strontium Sr 38 87.62
Gallium Ga 31 69.723 Sulfur S 16 32.06
Germanium Ge 32 72.63 Tantalum Ta 73 180.94788
Gold Au 79 196.966569 Technetium Tc 43 (98)
Hafnium Hf 72 178.49 Tellurium Te 52 127.60
Hassium Hs 108 (277) Terbium Tb 65 158.92535
Helium He 2 4.002602 Thallium Tl 81 204.38
Holmium Ho 67 164.93032 Thorium Th 90 232.03806
Hydrogen H 1 1.008 Thulium Tm 69 168.93421
Indium In 49 114.818 Tin Sn 50 118.710
Iodine I 53 126.90447 Titanium Ti 22 47.867
Iridium Ir 77 192.217 Tungsten W 74 183.84
Iron Fe 26 55.845 Ununoctium Uuo 118 (294)
Krypton Kr 36 83.798 Ununpentium Uup 115 (288)
Lanthanum La 57 138.90547 Ununseptium Uus 117 (294)
Lawrencium Lr 103 (262) Ununtrium Uut 113 (284)
Lead Pb 82 207.2 Uranium U 92 238.02891
Lithium Li 3 6.94 Vanadium V 23 50.9415
Livermorium Lv 116 (293) Xenon Xe 54 131.293
Lutetium Lu 71 174.9668 Ytterbium Yb 70 173.054
Magnesium Mg 12 24.3050 Yttrium Y 39 88.90585
Manganese Mn 25 54.938045 Zinc Zn 30 65.38
Meitnerium Mt 109 (276) Zirconium Zr 40 91.224
The values given in parentheses are the atomic mass numbers of the isotopes of the longest known half-life. From M. E. Wieser and T. B.
Coplen, Pure Appl. Chem., 2011, 83(2), 359–96, DOI: 10.1351/PAC-REP-10-09-14.
Molar Masses of Some Compounds
Compound Molar Mass Compound Molar Mass
AgBr 187.772 K3Fe(CN)6 329.248
AgCl 143.32 K4Fe(CN)6 368.346
Ag2CrO4 331.729 KHC8H4O4 (phthalate) 204.222
AgI 234.7727 KH(IO3)2 389.909
AgNO3 169.872 K2HPO4 174.174
AgSCN 165.95 KH2PO4 136.084
Al2O3 101.960 KHSO4 136.16
Al2(SO4)3 342.13 KI 166.0028
As2O3 197.840 KIO3 214.000
B2O3 69.62 KIO4 229.999
BaCO3 197.335 KMnO4 158.032
BaCl2 ? 2H2O 244.26 KNO3 101.102
BaCrO4 253.319 KOH 56.105
Ba(IO3)2 487.130 KSCN 97.18
Ba(OH)2 171.341 K2SO4 174.25
BaSO4 233.38 La(IO3)3 663.610
Bi2O3 465.958 Mg(C9H6NO)2 312.611
CO2 44.009 (8-hydroxyquinolate)
CaCO3 100.086 MgCO3 84.313
CaC2O4 128.096 MgNH4PO4 137.314
CaF2 78.075 MgO 40.304
CaO 56.077 Mg2P2O7 222.551
CaSO4 136.13 MgSO4 120.36
Ce(HSO4)4 528.37 MnO2 86.936
CeO2 172.114 Mn2O3 157.873
Ce(SO4)2 332.23 Mn3O4 228.810
(NH4)2Ce(NO3)6 548.22 Na2B4O7 ? 10H2O 381.36
(NH4)4Ce(SO4)4 ? 2H2O 632.53 NaBr 102.894
Cr2O3 151.989 NaC2H3O2 82.034
CuO 79.545 Na2C2O4 133.998
Cu2O 143.091 NaCl 58.44
CuSO4 159.60 NaCN 49.008
Fe(NH4)2(SO4)2 ? 6H2O 392.13 Na2CO3 105.988
FeO 71.844 NaHCO3 84.006
Fe2O3 159.687 Na2H2EDTA ? 2H2O 372.238
Fe3O4 231.531 Na2O2 77.978
HBr 80.912 NaOH 39.997
HC2H3O2 (acetic acid) 60.052 NaSCN 81.07
HC7H5O2 (benzoic acid) 122.123 Na2SO4 142.04
(HOCH2)3CNH2 (TRIS) 121.135 Na2S2O3 ? 5H2O 248.17
HCl 36.46 NH4Cl 53.49
HClO4 100.45 (NH4)2C2O4 ? H2O 142.111
H2C2O4 ? 2H2O 126.064 NH4NO3 80.043
H5IO6 227.938 (NH4)2SO4 132.13
HNO3 63.012 (NH4)2S2O8 228.19
H2O 18.015 NH4VO3 116.978
H2O2 34.014 Ni(C4H7O2N2)2 288.917
H3PO4 97.994 (dimethylglyoximate)
H2S 34.08 PbCrO4 323.2
H2SO3 82.07 PbO 223.2
H2SO4 98.07 PbO2 239.2
HgO 216.59 PbSO4 303.3
Hg2Cl2 472.08 P2O5 141.943
HgCl2 271.49 Sb2S3 339.70
KBr 119.002 SiO2 60.083
KBrO3 166.999 SnCl2 189.61
KCl 74.55 SnO2 150.71
KClO3 122.55 SO2 64.06
KCN 65.116 SO3 80.06
K2CrO4 194.189 Zn2P2O7 304.70
K2Cr2O7 294.182
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Charles D. Winters
H2O 1 I32(aq) 1 H3AsO3(aq) S d 3I2(aq) 1 H3AsO4(aq) 1 H1(aq)
(a) (b)
Color Plate 1 Chemical Equilibrium 1: Reaction between iodine and
arsenic(III) at pH 1. (a) One mmol I3− added to one mmol H3AsO3.
(b) Three mmol I− added to one mmol H3AsO4. Both combinations of
solutions produce the same final equilibrium state (see Section 9B-1, page 202).
Charles D. Winters
H2O 1 I32(aq) 1 H3AsO3(aq) S d 3I2(aq) 1 H3AsO4(aq) 1 H1(aq)

(a) (b)
Color Plate 2 Chemical Equilibrium 2: The same reaction as in color
plate 1 carried out at pH 7, producing a different equilibrium state than that
in Color Plate 1, and although similar to the situation in Color Plate 1, the
same state is produced from either the forward (a) or the reverse (b) direction
(see Section 9B-1, page 202).
Charles D. Winters
I32(aq) 1 2Fe(CN)64−(aq) S d 3I2(aq) 1 2Fe(CN)63− (aq)

(a) (b)
Color Plate 3 Chemical Equilibrium 3: Reaction between iodine and
ferrocyanide. (a) One mmol I3− added to two mmol Fe(CN)642. (b) Three
mmol I− added to two mmol Fe(CN)632. Both combinations of solutions
produce the same final equilibrium state. (see Section 9B-1, page 202).
Color Plate 5 Crystallization of sodium acetate from
a supersaturated solution (see Section 12A-2, page 280).
A tiny seed crystal is dropped into the center of a petri dish
containing a supersaturated solution of the compound.
The time sequence of photos taken about once per second
shows the growth of the beautiful crystals of sodium acetate.
Charles D. Winters
Charles D. Winters
Charles D. Winters
Charles D. Winters
Charles D. Winters
Color Plate 4 The common-ion effect.

The test tube on the left contains a saturated
solution of silver acetate, AgOAc. The following
equilibrium is established in the test tube:
AgOAc(s) 8 Ag+(aq) + OAc−(aq)
When AgNO3 is added to the test tube, the
Charles D. Winters
equilibrium shifts to the left to form more

AgOAc, as shown in the test tube on the right
(see Section 9B-5, page 209).
Color Plate 6 The Tyndall effect. The photo shows
two cuvettes: the one on the left contains only water while
the one on the right contains a solution of starch. As red
and green laser beams pass through the water in the left
cuvette, they are invisible. Colloidal particles in the starch
solution in the right cuvette scatter the light from the two
lasers, so the beams become visible (see Section 12A-2,
margin note, page 280).
Charles D. Winters
Color Plate 7 When dimethylglyoxime

is added to a slightly basic solution of
Ni21(aq), shown on the left, a bright red
precipitate of Ni(C4H7N2O2)2 is formed
as seen in the beaker on the right
(see Section 12C-3, page 294).
Charles D. Winters
1 2 3 4 5 6 7 8 9 10 11 12 1 2 3 4 5 6 7 8 9 10 11 12
pH pH
Methyl violet (0.0–1.6) Chlorophenol red (4.8–6.7)
1 2 3 4 5 6 7 8 9 10 11 12 1 2 3 4 5 6 7 8 9 10 11 12
pH pH
Bromophenol blue (3.0–4.6) m-Cresol purple (7.4–9.0)
1 2 3 4 5 6 7 8 9 10 11 12 1 2 3 4 5 6 7 8 9 10 11 12
pH pH
Methyl orange (3.2–4.4) Thymol blue (8.0–9.2)
1 2 3 4 5 6 7 8 9 10 11 12 1 2 3 4 5 6 7 8 9 10 11 12
pH pH
Bromocresol green (3.8–5.4) Phenolphthalein (8.0–10.0)
1 2 3 4 5 6 7 8 9 10 11 12 1 2 3 4 5 6 7 8 9 10 11 12
pH pH
Alizarin red (4.6–6.0) o-Cresolphthalein (8.2–9.8)
Charles D. Winters
1 2 3 4 5 6 7 8 9 10 11 12 1 2 3 4 5 6 7 8 9 10 11 12
pH pH
Bromothymol (6.0–7.0) Thymolphthalein (8.8–10.5)
Color Plate 8 Acid/base indicators and their transition pH ranges (see Section 14A-2, page 323).
Charles D. Winters
Charles D. Winters
Color Plate 9 End point in an acid/base titration with phenolphthalein as Color Plate 10 Reduction of
indicator. The end point is achieved when the barely perceptible pink color of silver(I) by direct reaction with
phenolphthalein persists. The flask on the left shows the titration less than half a copper, forming the “silver tree”
drop prior to the end point; the middle flask shows the end point. The flask on (see Section 18A-2, page 445).
the right shows what happens when a slight excess of base is added to the titra-
tion mixture. The solution turns a deep pink color, and the end point has been
exceeded (see Section 13A-1, page 304).
Charles D. Winters
2Fe31 1 3I2 8 2Fe21 1 I32
Color Plate 12 Reaction between Iron(III) and

Charles D. Winters
iodide. The species in each beaker are indicated by

the colors of the solutions. Iron (III) is pale yellow,
iodide is colorless, and triiodide is intense red-
orange (see margin note, Section 18C-6, page 464).
Color Plate 11 A modern version of the Daniell Cell
(see Feature 18-2, page 450).
Charles D. Winters
Charles D. Winters
Charles D. Winters
Color Plate 13 The time dependence of the reaction between permanganate and oxalate (see Section 20C-1, page 515).
© H&H Productions
(a)
Simon Tulloch
Simon Tulloch
(b) (c)
Color Plate 14 (a) Typical linear CCD arrays for spectrophotometers. The array on the right has 4096 pixels, and the
array on the left has 2048 pixels. In both arrays, each pixel has the dimensions of 14 mm 3 14 mm. These devices have a
spectral range of 200-1000 nm, a dynamic range of 2500:1 (see Section 8E-2), and are available with low-cost glass or
UV-enhanced fused silica windows. In addition to the sizes shown, the arrays are available in lengths of 512 and 1024 pixels.
(b) Photomicrograph of a section of a two-dimensional CCD array that is used for imaging and spectroscopy. Light falling
on the millions of pixels in the upper left of the photo creates charge that is transferred to the vertical channels at the
bottom of the photo and shifted from left to right along the string of channels until it reaches the output amplifier section
shown in (c). The amplifier provides a voltage proportional to the charge accumulated on each pixel, which is in turn
proportional to the intensity of light falling on the pixel (see Section 25A-4, page 705, for a discussion of charge-transfer
devices).
Color Plate 15 Series of standards (left) and two

unknowns (right) for the spectrophotometric determina-
tion of Fe(II) using 1,10-phenanthroline as reagent
(see Section 26A-3 and Problem 26-26, page 757).
The color is due to the complex Fe(phen)32+.
The absorbance of the standards is measured, and a
working curve is analyzed using linear least-squares
Charles D. Winters
(see Section 8C-2, page 172). The equation for the

line is then used to determine the concentrations of the
unknown solutions from their measured absorbances.
Visible Spectrum
380 400 420 440 460 480 500 520 540 560 580 600 620 640 660 680 700 720
Barium
380 400 420 440 460 480 500 520 540 560 580 600 620 640 660 680 700 720
Calcium
380 400 420 440 460 480 500 520 540 560 580 600 620 640 660 680 700 720
Chromium
380 400 420 440 460 480 500 520 540 560 580 600 620 640 660 680 700 720
Europium
380 400 420 440 460 480 500 520 540 560 580 600 620 640 660 680 700 720
Indium
380 400 420 440 460 480 500 520 540 560 580 600 620 640 660 680 700 720
Iron
380 400 420 440 460 480 500 520 540 560 580 600 620 640 660 680 700 720
Lithium
380 400 420 440 460 480 500 520 540 560 580 600 620 640 660 680 700 720
Sodium
380 400 420 440 460 480 500 520 540 560 580 600 620 640 660 680 700 720
Strontium
380 400 420 440 460 480 500 520 540 560 580 600 620 640 660 680 700 720
Thallium
380 400 420 440 460 480 500 520 540 560 580 600 620 640 660 680 700 720
Vanadium
380 400 420 440 460 480 500 520 540 560 580 600 620 640 660 680 700 720
Ytterbium
Jim Holler
380 400 420 440 460 480 500 520 540 560 580 600 620 640 660 680 700 720
l, nm
Color Plate 16 Spectrum of white light and emission spectra of selected elements
(see Chapter 28).
400 410 420 430 440 450 460
460 470 480 490 500 510 520
520 530 540 550 560 570 580
580 590 600 610 620 630 640
640 650 660 670 680 690 700
l, nm
(a)
He
Fe (Dr. Donald Mickey)
(a)
Color Plate 17 The solar spectrum. (a) Expanded color version of the solar spectrum
shown in black and white in Feature 24-1 (see Figure 24F-1, page 657). The huge number
of dark absorption lines are produced by all of the elements in the sun. See if you can
spot some prominent lines like the famous sodium doublet. (b) Compact version of the
solar spectrum in (a) compared to the emission spectra of hydrogen, helium, and iron.
It is relatively easy to spot lines in the emission spectra of hydrogen and iron that
correspond to absorption lines in the solar spectrum, but the lines of helium are quite
obscure. In spite of this problem, helium was discovered when these lines were observed
in the solar spectrum (see Section 28D). (Images created by Dr. Donald Mickey,
University of Hawaii Institute for Astronomy from National Solar Observatory spectral
data/NSO/Kitt Peak FTS data by NSF/NOAO.)
Color Plate 18 (a) Demonstration
of atomic absorption by mercury vapor.
(b) White light from the source on the
right passes through the mercury vapor
above the flask and no shadow appears
on the fluorescent screen on the left.
Light from the mercury lamp on the
left containing the characteristic UV
lines of the element is absorbed by the
vapor in and above the flask, which casts
a shadow on the screen on the right of
the plume of mercury vapor (see Section
28D-4, page 797).
Charles D. Winters
(a)
Fluorescent screen Shadow
Liquid Mercury vapor

mercury
Jim Holler
Mercury vapor lamp White light source

(b)
Charles D. Winters
Charles D. Winters
(a) (b)
Charles D. Winters
Charles D. Winters
(c) (d)
Color Plate 19 Weighing by

difference the old-fashioned way.
(a) Zero the balance. (b) Place a
weighing bottle containing the
solute on the balance pan. (c) Read
the mass (33.2015 g). (d) Transfer
the desired amount of solute to a flask.
(e) Replace the weighing bottle on the
pan and read the mass (33.0832 g).
Finally, calculate the mass of the
solute transferred to the flask:
33.2015 g 2 33.0832 g 5 0.1131 g
(see Section 2E-4, page 27).
(Electronic balance provided by
Charles D. Winters
Mettler-Toledo, Inc.)
(e)
Color Plate 20 Weighing by differ-
ence the modern way. Place a weighing
bottle containing the solute on the
balance pan and (a) depress the tare
or zero button. The balance should
then read 0.0000 g, as shown in (b).
(c) Transfer the desired amount of
solute to a flask. Replace the weighing
bottle on the pan, and (d) the balance
reads the decrease in mass directly as
20.1070 g (see Section 2E-4, page 27).
Many modern balances have built-in
computers with programs to perform a
variety of weighing tasks. For example,
it is possible to dispense many
Charles D. Winters
Charles D. Winters
consecutive quantities of a substance
and automatically read out the loss in
mass following each dispensing.
Many balances also have computer
(a) (b) intterfaces so that reading may be
logged directly to programs running
on the computer. (Electronic balance
provided by Mettler-Toledo, Inc.)
Charles D. Winters
Charles D. Winters
(c) (d)
1020 1019 1018 1017 1016 1015 1014 1013 1012 1011 1010 Frequency (s21)
Far Near
Gamma Near Far TV FM AM
X rays ultra- ultra- Microwaves Radar
rays infrared infrared Radio waves
Visible
violet violet
10212 10211 10210 1029 1028 1027 1026 1025 1024 1023 1022 1021 Wavelength (m)
(1 pm) (10 pm) (100 pm) (1 nm) (10 nm) (100 nm) (1 mm) (10 mm) (100 mm) (1 mm) (10 mm) (100 mm)
Visible spectrum
350 400 450 500 550 600 650 700 750 800
nm
Color Plate 21 Electromagnetic spectrum. The spectrum extends from high-energy (frequency) gamma rays to low-energy (frequency) radio waves (see
Section 24B-1, page 654). Note that the visible region is only a tiny fraction of the spectrum. The visible region, broken out in the lower portion, e xtends
from the violet (≈380 nm) to the red region (≈800 nm). (Courtesy of Ebbing and Gammon, General Chemistry, 10th ed.)
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Fundamentals of
Analytical
Chemistry ninth Edition
Douglas A. Skoog
Stanford University
Donald M. West
San Jose State University
F. James Holler
University of Kentucky
Stanley R. Crouch
Michigan State University
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1 2 3 4 5 6 7 16 15 14 13 12
Contents in Brief
Chapter 1 The Nature of Analytical Chemistry 1
Part I Tools of Analytical Chemistry 14

Chapter 2 Chemicals, Apparatus, and Unit Operations of
Analytical Chemistry 15
Chapter 3 Using Spreadsheets in Analytical Chemistry 48
Chapter 4 Calculations Used in Analytical Chemistry 62
Chapter 5 Errors in Chemical Analyses 82
Chapter 6 Random Errors in Chemical Analysis 93
Chapter 7 Statistical Data Treatment and Evaluation 123
Chapter 8 Sampling, Standardization, and Calibration 153
Part II Chemical Equilibria 196

Chapter 9 Aqueous Solutions and Chemical Equilibria 197
Chapter 10 Effect of Electrolytes on Chemical Equilibria 235
Chapter 11 Solving Equilibrium Problems for
Complex Systems 249
Part III Classical Methods of Analysis 279

Chapter 12 Gravimetric Methods of Analysis 280
Chapter 13 Titrations in Analytical Chemistry 302
Chapter 14 Principles of Neutralization Titrations 322
Chapter 15 Complex Acid/Base Systems 348
Chapter 16 Applications of Neutralization Titrations 381
Chapter 17 Complexation and Precipitation Reactions
and Titrations 400
Part IV Electrochemical Methods 441

Chapter 18 Introduction to Electrochemistry 442
Chapter 19 Applications of Standard Electrode Potentials 473
Chapter 20 Applications of Oxidation/Reduction Titrations 509
Chapter 21 Potentiometry 535
Chapter 22 Bulk Electrolysis: Electrogravimetry and Coulometry 578
Chapter 23 Voltammetry 610
Part V Spectrochemical Methods 649

Chapter 24 Introduction to Spectrochemical Methods 650
Chapter 25 Instruments for Optical Spectrometry 683
Chapter 26 Molecular Absorption Spectrometry 722
Chapter 27 Molecular Fluorescence Spectroscopy 760
Chapter 28 Atomic Spectroscopy 773
Chapter 29 Mass Spectrometry 802
iii
iv Contents in Brief
Part VI Kinetics and Separations 818

Chapter 30 Kinetic Methods of Analysis 819
Chapter 31 Introduction to Analytical Separations 847
Chapter 32 Gas Chromatography 887
Chapter 33 High-Performance Liquid Chromatography 912
Chapter 34 Miscellaneous Separation Methods 935
Part VII Practical Aspects of Chemical Analysis 959

Part VII chapters are only available as an Adobe Acrobat® PDF file on the web at
www.cengage.com/chemistry/skoog/fac9.
Chapter 35 The Analysis of Real Samples 960

Chapter 36 Preparing Samples for Analysis 970
Chapter 37 Decomposing and Dissolving the Sample 976
Chapter 38 Selected Methods of Analysis 986
Glossary G-1
Appendix 1 The Literature of Analytical Chemistry A-1
Appendix 2 Solubility Product Constants at 25°C A-6
Appendix 3 Acid Dissociation Constants at 25°C A-8
Appendix 4 Formation Constants at 25°C A-10
Appendix 5 Standard and Formal Electrode Potentials A-12
Appendix 6 Use of Exponential Numbers and Logarithms A-15
Appendix 7 Volumetric Calculations Using Normality and Equivalent
Weight A-19
Appendix 8 Compounds Recommended for the Preparation of Standard
Solutions of Some Common Elements A-27
Appendix 9 Derivation of Error Propagation Equations A-29
Answers to Selected Questions and Problems A-34

Index I-1
Contents
Chapter 1 The Nature of Analytical Chemistry 1 Chapter 6 Random Errors in Chemical Analysis 93
1A The Role of Analytical Chemistry 2 6A The Nature of Random Errors 93
1B Quantitative Analytical Methods 4 Feature 6-1 Flipping Coins: A Student Activity to Illustrate a
1C A Typical Quantitative Analysis 4 Normal Distribution 97
1D An Integral Role for Chemical Analysis: 6B Statistical Treatment of Random Errors 98
Feedback Control Systems 9 Feature 6-2 Calculating the Areas under the Gaussian
Feature 1-1 Deer Kill: A Case Study Illustrating the Use Curve 101
of Analytical Chemistry to Solve a Problem Feature 6-3 The Significance of the Number of Degrees of
in Toxicology 10 Freedom 104
Feature 6-4 Equation for Calculating the Pooled Standard
Tools of Analytical
PART I Deviation 107
Chemistry 14 6C Standard Deviation of Calculated Results 110
Chapter 2 Chemicals, Apparatus, and Unit Operations of 6D Reporting Computed Data 115
Analytical Chemistry 15
2A Selecting and Handling Reagents Chapter 7 Statistical Data Treatment and Evaluation 123
and Other Chemicals 16 7A Confidence Intervals 124
2B Cleaning and Marking Feature 7-1 W. S. Gossett (“Student”) 127
of Laboratory Ware 17 7B Statistical Aids to Hypothesis Testing 129
2C Evaporating Liquids 18 7C Analysis of Variance 140
2D Measuring Mass 18 7D Detection of Gross Errors 146
2E Equipment and Manipulations
Associated with Weighing 25 Chapter 8 Sampling, Standardization,
2F Filtration and Ignition of Solids 28 and Calibration 153
2G Measuring Volume 34 8A Analytical Samples and Methods 153
2H Calibrating Volumetric Glassware 43 8B Sampling 156
2I The Laboratory Notebook 45 8C Automated Sample Handling 164
2J Safety in the Laboratory 46 8D Standardization and Calibration 167
Feature 8-1 Lab-on-a-Chip 168
Chapter 3 Using Spreadsheets in Feature 8-2 A Comparison Method for Aflatoxins 169
Analytical Chemistry 48 Feature 8-3 Multivariate Calibration 180
3A Keeping Records and Making Calculations 49 8E Figures of Merit for Analytical Methods 186
3B More Complex Examples 52
PART II Chemical Equilibria 196
Chapter 4 Calculations Used
Chapter 9 Aqueous Solutions and Chemical
in Analytical Chemistry 62
Equilibria 197
4A Some Important Units of Measurement 62
9A The Chemical Composition of Aqueous Solutions 197
Feature 4-1 Unified Atomic Mass Units and the Mole 65
9B Chemical Equilibrium 202
Feature 4-2 The Factor-Label Approach
to Example 4-2 67 Feature 9-1 Stepwise and Overall Formation Constants for
Complex Ions 205
4B Solutions and Their Concentrations 67
Feature 9-2 Why [H2O] Does Not Appear in Equilibrium-
4C Chemical Stoichiometry 75 Constant Expressions for Aqueous Solutions 206
Chapter 5 Errors in Chemical Analyses 82 Feature 9-3 Relative Strengths of Conjugate Acid/Base Pairs 212
Feature 9-4 The Method of Successive Approximations 217
5A Some Important Terms 84
5B Systematic Errors 87 9C Buffer Solutions 219
v
vi Contents
Feature 9-5 The Henderson-Hasselbalch Equation 221 Chapter 15 Complex Acid/Base Systems 348
Feature 9-6 Acid Rain and the Buffer Capacity of Lakes 227 15A Mixtures of Strong and Weak Acids or Strong and
Weak Bases 348
Chapter 10 Effect of Electrolytes on Chemical 15B Polyfunctional Acids and Bases 352
Equilibria 235 15C Buffer Solutions Involving Polyprotic Acids 354
10A The Effect of Electrolytes on Chemical Equilibria 235 15D Calculation of the pH of Solutions of NaHA 356
10B Activity Coefficients 239 15E Titration Curves for Polyfunctional Acids 360
Feature 10-1 Mean Activity Coefficients 242 Feature 15-1 The Dissociation of Sulfuric Acid 368
15F Titration Curves for Polyfunctional Bases 369
Chapter 11 Solving Equilibrium Problems for Complex
Systems 249 15G Titration Curves for Amphiprotic Species 371
11A Solving Multiple-Equilibrium Problems Using a Feature 15-2 Acid/Base Behavior of Amino Acids 371
Systematic Method 250 15H Composition of Polyprotic Acid Solutions as a Function
11B Calculating Solubilities by the Systematic Method 256 of pH 373
Feature 11-1 Algebraic Expressions Needed to Calculate the Feature 15-3 A General Expression for Alpha Values 374
Solubility of CaC2O4 in Water 262 Feature 15-4 Logarithmic Concentration Diagrams 375
11C Separation of Ions by Control of the Concentration of the
Precipitating Agent 268 Chapter 16 Applications of Neutralization Titrations 381
Feature 11-2 Immunoassay: Equilibria in the Specific 16A Reagents for Neutralization Titrations 382
Determination of Drugs 272 16B Typical Applications of Neutralization Titrations 387
Feature 16-1 Determining Total Serum Protein 388
Feature 16-2 Other Methods for Determining
part III Classical Methods
Organic Nitrogen 388
of Analysis 279
Feature 16-3 Equivalent Masses of Acids and Bases 394
Chapter 12 Gravimetric Methods of Analysis 280
12A Precipitation Gravimetry 280 Chapter 17 Complexation and Precipitation Reactions
Feature 12-1 Specific Surface Area of Colloids 287 and Titrations 400
12B Calculation of Results from Gravimetric Data 291 17A The Formation of Complexes 400
12C Applications of Gravimetric Methods 294 Feature 17-1 Calculation of Alpha Values for Metal
Complexes 403
Chapter 13 Titrations in Analytical Chemistry 302 17B Titrations with Inorganic Complexing Agents 406
13A Some Terms Used in Volumetric Titrations 303 Feature 17-2 Determination of Hydrogen Cyanide in
13B Standard Solutions 305 Acrylonitrile Plant Streams 407
13C Volumetric Calculations 306 17C Organic Complexing Agents 413
Feature 13-1 Another Approach to Example 13-6(a) 311 17D Aminocarboxylic Acid Titrations 414
Feature 13-2 Rounding the Answer to Example 13-7 312 Feature 17-3 Species Present in a Solution of EDTA 415
13D Gravimetric Titrations 314 Feature 17-4 EDTA as a Preservative 418
13E Titration Curves 315 Feature 17-5 EDTA Titration Curves When a Complexing Agent
Feature 13-3 Calculating the NaOH Volumes Shown in the First Is Present 428
Column of Table 13-1 317 Feature 17-6 Enhancing the Selectivity of EDTA Titrations with
Masking and Demasking Agents 435
Chapter 14 Principles of Neutralization Titrations 322 Feature 17-7 Test Kits for Water Hardness 436
14A Solutions and Indicators for Acid/Base Titrations 322
14B Titration of Strong Acids and Bases 326 PART IV Electrochemical
Feature 14-1 Using the Charge-balance Equation to Construct
Methods 441
Titration Curves 328 Chapter 18 Introduction to Electrochemistry 442
Feature 14-2 Significant Figures in Titration Curve 18A Characterizing Oxidation/Reduction Reactions 442
Calculations 331 Feature 18-1 Balancing Redox Equations 444
14C Titration Curves for Weak Acids 332 18B Electrochemical Cells 446
Feature 14-3 Determining Dissociation Constants of Weak Acids Feature 18-2 The Daniell Gravity Cell 450
and Bases 334 18C Electrode Potentials 451
Feature 14-4 A Master Equation Approach to Weak Acid/Strong Feature 18-3 Why We Cannot Measure Absolute Electrode
Base Titrations 336 Potentials 456
14D Titration Curves for Weak Bases 337 Feature 18-4 Sign Conventions in the Older Literature 464
Feature 14-5 Determining the pK Values for Amino Acids 339 Feature 18-5 Why Are There Two Electrode Potentials for Br2 in
14E The Composition of Solutions During Acid/Base Table 18-1? 466
Titrations 341
Feature 14-6 Locating Titration End Points from
pH Measurements 342
Contents vii
Chapter 19 Applications of Standard Electrode Feature 23-1 Voltammetric Instruments Based on Operational
Potentials 473 Amplifiers 613
19A Calculating Potentials of Electrochemical Cells 473 23C Hydrodynamic Voltammetry 618
19B Determining Standard Potentials Experimentally 480 23D Polarography 633
Feature 19-1 Biological Redox Systems 482 23E Cyclic Voltammetry 635
19C Calculating Redox Equilibrium Constants 482 23F Pulse Voltammetry 639
Feature 19-2 A General Expression for Calculating Equilibrium 23G Applications of Voltammetry 642
Constants from Standard Potentials 487 23H Stripping Methods 643
19D Constructing Redox Titration Curves 488 23I Voltammetry with Microelectrodes 645
Feature 19-3 The Inverse Master Equation Approach for Redox
Titration Curves 497 PART V Spectrochemical Analysis 649
Feature 19-4 Reaction Rates and Electrode Potentials 502 Chapter 24 Introduction to Spectrochemical
19E Oxidation/Reduction Indicators 502 Methods 650
19F Potentiometric End Points 505 24A Properties of Electromagnetic Radiation 651
24B Interaction of Radiation and Matter 654
Chapter 20 Applications of Oxidation/Reduction Feature 24-1 Spectroscopy and the Discovery of Elements 657
Titrations 509 24C Absorption of Radiation 658
20A Auxiliary Oxidizing and Reducing Reagents 509 Feature 24-2 Deriving Beer’s Law 660
20B Applying Standard Reducing Agents 511 Feature 24-3 Why Is a Red Solution Red? 665
20C Applying Standard Oxidizing Agents 515 2D Emission of Electromagnetic Radiation 674
Feature 20-1 Determination of Chromium Species in Water
Samples 517 Chapter 25 Instruments for Optical Spectrometry 683
Feature 20-2 Antioxidants 522 25A Instrument Components 683
Feature 25-1 Laser Sources: The Light Fantastic 687
Chapter 21 Potentiometry 535 Feature 25-2 Origin of Equation 25-1 693
21A General Principles 536
Feature 25-3 Producing Ruled and Holographic Gratings 695
21B Reference Electrodes 537
Feature 25-4 Basis of Equation 25-2 698
21C Liquid-Junction Potentials 539
Feature 25-5 Signals, Noise, and the Signal-to-Noise
21D Indicator Electrodes 540 Ratio 700
Feature 21-1 An Easily Constructed Liquid-Membrane Feature 25-6 Measuring Photocurrents with Operational
Ion-Selective Electrode 552 Amplifiers 708
Feature 21-2 The Structure and Performance of Ion-Sensitive 25B Ultraviolet/Visible Photometers and
Field Effect Transistors 554 Spectrophotometers 710
Feature 21-3 Point-of-Care Testing: Blood Gases, and Blood 25C Infrared Spectrophotometers 713
Electrolytes with Portable Instrumentation 558
Feature 25-7 How Does a Fourier Transform Infrared
21E Instruments for Measuring Cell Potential 560 Spectrometer Work? 715
Feature 21-4 The Loading Error in Potential
Measurements 560 Chapter 26 Molecular Absorption Spectrometry 722
Feature 21-5 Operational Amplifier Voltage Measurements 562 26A Ultraviolet and Visible Molecular Absorption
21F Direct Potentiometry 563 Spectroscopy 722
21G Potentiometric Titrations 569 26B Automated Photometric and Spectrophotometric
21H Potentiometric Determination of Equilibrium Methods 744
Constants 573 26C Infrared Absorption Spectroscopy 746
Feature 26-1 Producing Spectra with an FTIR
Chapter 22 Bulk Electrolysis: Electrogravimetry and Spectrometer 751
Coulometry 578
22A The Effect of Current on Cell Potential 579
Chapter 27 Molecular Fluorescence Spectroscopy 760
Feature 22-1 Overvoltage and the Lead/Acid Battery 586 27A Theory of Molecular Fluorescence 760
22B The Selectivity of Electrolytic Methods 586 27B Effect of Concentration on Fluorescence Intensity 764
22C Electrogravimetric Methods 588 27C Fluorescence Instrumentation 765
22D Coulometric Methods 594 27D Applications of Fluorescence Methods 766
Feature 27-1 Use of Fluorescence Probes in Neurobiology:
Feature 22-2 Coulometric Titration of Chloride in
Biological Fluids 603 Probing the Enlightened 767
27E Molecular Phosphorescence Spectroscopy 769
Chapter 23 Voltammetry 610 27F Chemiluminescence Methods 770
23A Excitation Signals in Voltammetry 611
23B Voltammetric Instrumentation 612
viii Contents
Chapter 28 Atomic Spectroscopy 773 Chapter 34 Miscellaneous Separation Methods 935

28A Origins of Atomic Spectra 774 34A Supercritical Fluid Separations 935
28B Production of Atoms and Ions 776 34B Planar Chromatography 940
28C Atomic Emission Spectrometry 786 34C Capillary Electrophoresis 942
28D Atomic Absorption Spectrometry 790 Feature 34-1 Capillary Array Electrophoresis in DNA
Feature 28-1 Determining Mercury by Cold-Vapor Atomic Sequencing 949
Absorption Spectroscopy 797 34D Capillary Electrochromatography 949
28E Atomic Fluorescence Spectrometry 799 34E Field-Flow Fractionation 952
Chapter 29 Mass Spectrometry 802 PART VII Practical Aspects

29A Principles of Mass Spectrometry 802 of Chemical Analysis 959
29B Mass Spectrometers 804 The following chapters are available as Adobe Acrobat®
29C Atomic Mass Spectrometry 808 PDF files at www.cengage.com/chemistry/skoog/fac9.
29D Molecular Mass Spectrometry 811
Chapter 35 The Analysis of Real Samples 960
PART VI Kinetics and Separations 818 35A Real Samples 960
Chapter 30 Kinetic Methods of Analysis 819 35B Choice of Analytical Method 962
30A Rates of Chemical Reactions 820 35C Accuracy in the Analysis of Complex Materials 967
Feature 30-1 Enzymes 827
30B Determining Reaction Rates 833 Chapter 36 Preparing Samples for Analysis 970
Feature 30-2 Fast Reactions and Stopped-Flow Mixing 833 36A Preparing Laboratory Samples 970
30C Applications of Kinetic Methods 840 36B Moisture in Samples 972
Feature 30-3 The Enzymatic Determination of Urea 842 36C Determining Water in Samples 975
Chapter 31 Introduction to Analytical Separations 847 Chapter 37 Decomposing and Dissolving the
31A Separation by Precipitation 848 Sample 976
31B Separation of Species by Distillation 852 37A Sources of Error in Decomposition and
Dissolution 977
31C Separation by Extraction 852
37B Decomposing Samples with Inorganic Acids in
Feature 31-1 Derivation of Equation 31-3 854
Open Vessels 977
31D Separating Ions by Ion Exchange 857 37C Microwave Decompositions 979
Feature 31-2 Home Water Softeners 860
37D Combustion Methods for Decomposing Organic
31E Chromatographic Separations 861 Samples 982
Feature 31-3 What Is the Source of the Terms Plate and 37E Decomposing Inorganic Materials with Fluxes 984
Plate Height? 871
Feature 31-4 Derivation of Equation 31-24 872 Chapter 38 Selected Methods of Analysis 986
38A An Introductory Experiment 987
Chapter 32 Gas Chromatography 887 38B Gravimetric Methods of Analysis 996
32A Instruments for Gas-Liquid Chromatography 888 38C Neutralization Titrations 1000
32B Gas Chromatographic Columns and Stationary Phases 897 38D Precipitation Titrations 1009
32C Applications of Gas-Liquid Chromatography 901 38E Complex-Formation Titrations with EDTA 1012
Feature 32-1 Use of GC/MS to Identify a Drug Metabolite
38F Titrations with Potassium Permanganate 1015
in Blood 903
38G Titrations with Iodine 1021
32D Gas-Solid Chromatography 909
38H Titrations with Sodium Thiosulfate 1023
Chapter 33 High-Performance Liquid 38I Titrations with Potassium Bromate 1026
Chromatography 912 38J Potentiometric Methods 1028
33A Instrumentation 913 38K Electrogravimetric Methods 1032
Feature 33-1 LC/MS and LC/MS/MS 920 38L Coulometric Titrations 1034
33B Partition Chromatography 921 38M Voltammetry 1036
33C Adsorption Chromatography 924 38N Methods Based on the Absorption of Radiation 1038
33D Ion Chromatography 925 38O Molecular Fluorescence 1042
33E Size-Exclusion Chromatography 927 38P Atomic Spectroscopy 1043
Feature 33-2 Buckyballs: The Chromatographic Separation 38Q Application of Ion-Exchange Resins 1046
of Fullerenes 929 38R Gas-Liquid Chromatography 1048
33F Affinity Chromatography 931
33G Chiral Chromatography 931
33H Comparison of High-Performance Liquid Chromatography
and Gas Chromatography 932
Contents ix
Glossary G-1 Appendix 7 Volumetric Calculations Using Normality and

Equivalent Weight A-19
Appendix 1 The Literature of Analytical Chemistry A-1
Appendix 8 Compounds Recommended for the
Appendix 2 Solubility Product Constants at 25°C A-6 Preparation of Standard Solutions of Some
Appendix 3 Acid Dissociation Constants at 25°C A-8 Common Elements A-27
Appendix 4 Formation Constants at 25°C A-10 Appendix 9 Derivation of Error Propagation
Appendix 5 Standard and Formal Electrode Equations A-29
Potentials A-12 Answers to Selected Questions and Problems A-34
Appendix 6 Use of Exponential Numbers and
Logarithms A-15 Index I-1
Preface
T he ninth edition of Fundamentals of Analytical Chemistry is an introductory

textbook designed primarily for a one- or two-semester course for chemistry ma-
jors. Since the publication of the eighth edition, the scope of analytical chemistry has
continued to evolve, and thus, we have included in this edition many applications
to biology, medicine, materials science, ecology, forensic science, and other related
fields. As in the previous edition, we have incorporated many spreadsheet applica-
tions, examples, and exercises. We have revised some older treatments to incorporate
contemporary instrumentation and techniques. In response to the comments
of many readers and reviewers, we have added a chapter on mass spectrometry
to provide detailed instruction on this vital topic as early as possible in the chemistry
curriculum. Our companion book, Applications of Microsoft® Excel in Analytical
Chemistry, 2nd ed., provides students with a tutorial guide for using spreadsheets in
analytical chemistry and introduces many additional spreadsheet operations.
We recognize that courses in analytical chemistry vary from institution to institution
and depend on the available facilities and instrumentation, the time allocated to ana-
lytical chemistry in the chemistry curriculum, and the unique instructional philosophies
of teachers. We have, therefore, designed the ninth edition of Fundamentals of Analytical
Chemistry so that instructors can tailor the text to meet their needs and students can
learn the concepts of analytical chemistry on several levels: in descriptions, in pictorials,
in illustrations, in interesting and relevant features, and in using online learning.
Since the production of the eighth edition of this text, the duties and responsi-
bilities for planning and writing a new edition have fallen to two of us (FJH and
SRC). While making the many changes and improvements cited above and in the
remainder of the preface, we have maintained the basic philosophy and organization
of the eight previous editions and endeavored to preserve the same high standards
that characterized those texts.
Objectives
The primary objective of this text is to provide a thorough background in the chemi-
cal principles that are particularly important to analytical chemistry. Second, we want
students to develop an appreciation for the difficult task of judging the accuracy
and precision of experimental data and to show how these judgments can be sharp-
ened by applying statistical methods to analytical data. Third, we aim to introduce a
broad range of modern and classic techniques that are useful in analytical chemistry.
Fourth, we hope that, with the help of this book, students will develop the skills nec-
essary to solve quantitative analytical problems and, where appropriate, use powerful
spreadsheet tools to solve problems, perform calculations, and create simulations of
chemical phenomena. Finally, we aim to teach laboratory skills that will give students
confidence in their ability to obtain high-quality analytical data and that will high-
light the importance of attention to detail in acquiring these data.
xi
xii Preface
Coverage and Organization

The material in this text covers both fundamental and practical aspects of chemi-
cal analysis. We have organized the chapters into Parts that group together related
topics. There are seven major Parts to the text that follow the brief introduction
in Chapter 1.
• Part I covers the tools of analytical chemistry and comprises seven chapters.
Chapter 2 discusses the chemicals and equipment used in analytical laboratories
and includes many photographs of analytical operations. Chapter 3 is a tutorial
introduction to the use of spreadsheets in analytical chemistry. Chapter 4 reviews
the basic calculations of analytical chemistry, including expressions of chemical
concentration and stoichiometric relationships. Chapters 5, 6, and 7 present
topics in statistics and data analysis that are important in analytical chemistry
and incorporate extensive use of spreadsheet calculations. Analysis of variance,
ANOVA, is included in Chapter 7, and Chapter 8 provides details about acquiring
samples, standardization, and calibration.
• Part II covers the principles and application of chemical equilibrium systems in
quantitative analysis. Chapter 9 explores the fundamentals of chemical equilib-
ria. Chapter 10 discusses the effect of electrolytes on equilibrium systems. The
systematic approach for attacking equilibrium problems in complex systems is
the subject of Chapter 11.
• Part III brings together several chapters dealing with classical gravimetric and
volumetric analytical chemistry. Gravimetric analysis is described in Chapter 12.
In Chapters 13 through 17, we consider the theory and practice of titrimetric
methods of analysis, including acid/base titrations, precipitation titrations, and
complexometric titrations. We take advantage of the systematic approach to
equilibria and the use of spreadsheets in the calculations.
• Part IV is devoted to electrochemical methods. After an introduction to elec-
trochemistry in Chapter 18, Chapter 19 describes the many uses of electrode
potentials. Oxidation/reduction titrations are the subject of Chapter 20, while
Chapter 21 presents the use of potentiometric methods to measure concentra-
tions of molecular and ionic species. Chapter 22 considers the bulk electrolytic
methods of electrogravimetry and coulometry, and Chapter 23 discusses voltam-
metric methods, including linear sweep and cyclic voltammetry, anodic stripping
voltammetry, and polarography.
• Part V presents spectroscopic methods of analysis. The nature of light and its
interaction with matter are explored in Chapter 24. Spectroscopic instruments
and their components are the topics covered in Chapter 25. The various applica-
tions of molecular absorption spectrometric methods are discussed in some detail
in Chapter 26, while Chapter 27 is concerned with molecular fluorescence spec-
troscopy. Chapter 28 covers various atomic spectrometric methods, including
plasma and flame emission methods and electrothermal and flame atomic absorp-
tion spectroscopy. Chapter 29 on mass spectrometry is new to this edition and
provides an introduction to ionization sources, mass analyzers, and ion detectors.
Both atomic and molecular mass spectrometry are included.
• Part VI includes five chapters dealing with kinetics and analytical separations.
We investigate kinetic methods of analysis in Chapter 30. Chapter 31 intro-
duces analytical separations including ion exchange and the various chromato-
graphic methods. Chapter 32 discusses gas chromatography, while high-perfor-
mance liquid chromatography is covered in Chapter 33. The final chapter in
this Part, Chapter 34, introduces some miscellaneous separation methods,
Preface xiii
including supercritical fluid chromatography, capillary electrophoresis, and

field-flow fractionation.
• The final Part VII consists of four chapters dealing with the practical aspects of
analytical chemistry. These chapters are published on our website at www.cengage
.com/chemistry/skoog/fac9. We consider real samples and compare them to
ideal samples in Chapter 35. Methods for preparing samples are discussed in
Chapter 36, while techniques for decomposing and dissolving samples are covered
in Chapter 37. The text ends with Chapter 38, which provides detailed procedures
for laboratory experiments that cover many of the principles and applications
discussed in previous chapters.
Flexibility
Because the text is divided into Parts, there is substantial flexibility in the use of
the material. Many of the Parts can stand alone or be taken in a different order. For
example, some instructors may want to cover spectroscopic methods prior to electro-
chemical methods or separations prior to spectroscopic methods.
HIGHLIGHTS
This edition incorporates many features and methods intended to enhance the
learning experience for the student and to provide a versatile teaching tool for
the instructor.
Important Equations. Equations that we feel are the most important have been
highlighted with a color screen for emphasis and ease of review.
Mathematical Level. Generally the principles of chemical analysis developed here
are based on college algebra. A few of the concepts presented require basic differential
and integral calculus.
Worked Examples. A large number of worked examples serve as aids in understand-
ing the concepts of analytical chemistry. In this edition, we title the examples for
easier identification. As in the eighth edition, we follow the practice of including
units in chemical calculations and using the factor-label method to check correct-
ness. The examples also are models for the solution of problems found at the end of
most of the chapters. Many of these use spreadsheet calculations as described next.
Where appropriate, solutions to the worked examples are clearly marked with the
word Solution for ease in identification.
Spreadsheet Calculations. Throughout the book we have introduced spreadsheets
for problem solving, graphical analysis, and many other applications. Microsoft Excel®
on the PC has been adopted as the standard for these calculations, but the instruc-
tions can be easily adapted to other spreadsheet programs and platforms. Many other
detailed examples are presented in our companion book, Applications of Microsoft®
Excel in Analytical Chemistry, 2nd ed. We have attempted to document each stand-alone
spreadsheet with working formulas and entries.
Spreadsheet Summaries. References to our companion book Applications of Microsoft®
Excel in Analytical Chemistry, 2nd ed., are given as Spreadsheet Summaries in the text.
These are intended to direct the user to examples, tutorials, and elaborations of the
text topics.
Questions and Problems. An extensive set of questions and problems is included at
the end of most chapters. Answers to approximately half of the problems are given
at the end of the book. Many of the problems are best solved using spreadsheets.
These are identified by a spreadsheet icon placed in the margin next to the
problem.
xiv Preface
Challenge Problems. Most of the chapters have a challenge problem at the end of
the regular questions and problems. Such problems are intended to be open-ended,
research-type problems that are more challenging than normal. These problems
may consist of multiple steps, dependent on one another, or may require library or
Web searches to find information. We hope that these challenge problems stimulate
discussion and extend the topics of the chapter into new areas. We encourage in-
structors to use them in innovative ways, such as for group projects, inquiry-driven
learning assignments, and case study discussions. Because many challenge problems
are open-ended and may have multiple solutions, we do not provide answers or ex-
planations for them.
Features. A series of boxed and highlighted Features are found throughout the
text. These essays contain interesting applications of analytical chemistry to the
modern world, derivation of equations, explanations of more difficult theoretical
points, or historical notes. Examples include, W. S. Gosset (“Student”) (Chapter 7),
Antioxidants (Chapter 20), Fourier Transform Spectroscopy (Chapter 25),
LC/MS/MS (Chapter 33), and Capillary Electrophoresis in DNA Sequencing
(Chapter 34).
Illustrations and Photos. We feel strongly that photographs, drawings, picto-
rials, and other visual aids greatly assist the learning process. Hence, we have
included new and updated visual materials to aid the student. Most of the draw-
ings are done in two colors to increase the information content and to highlight
important aspects of the figures. Photographs and color plates taken exclusively
for this book by renowned chemistry photographer Charles Winters are intended
to illustrate concepts, equipment, and procedures that are difficult to illustrate
with drawings.
Expanded Figure Captions. Where appropriate, we have attempted to make the
figure captions quite descriptive so that reading the caption provides a second level of
explanation for many of the concepts. In some cases, the figures can stand by them-
selves much in the manner of a Scientific American illustration.
Web Works. In most of the chapters we have included a brief Web Works feature at
the end of the chapter. In these features, we ask the student to find information on
the web, do online searches, visit the websites of equipment manufacturers, or solve
analytical problems. These Web Works and the links given are intended to stimu-
late student interest in exploring the information available on the World Wide Web.
The links will be updated regularly on our website, www.cengage.com/chemistry/
skoog/fac9.
Glossary. At the end of the book we have placed a glossary that defines the most
important terms, phrases, techniques, and operations used in the text. The glossary is
intended to provide students with a means for rapidly determining a meaning with-
out having to search through the text.
Appendixes and Endpapers. Included in the appendixes are an updated guide to the
literature of analytical chemistry; tables of chemical constants, electrode potentials,
and recommended compounds for the preparation of standard materials; sections on
the use of logarithms and exponential notation and normality and equivalents (terms
that are not used in the text itself ); and a derivation of the propagation of error equa-
tions. The endpapers of this book provide a full-color chart of chemical indicators, a
periodic table, a 2009 IUPAC table of atomic masses, and a table of molar masses of
compounds of particular interest in analytical chemistry based on the 2009 atomic
masses. In addition, included in the book is a tear-out reference card for the 2010
and 2007 versions of Microsoft Excel.
Preface xv
What’s New
Readers of the eighth edition will find numerous changes in the ninth edition in con-
tent as well as in style and format.
Content. Several changes in content have been made to strengthen the book.
• Many chapters have been strengthened by adding spreadsheet examples, applica-
tions, and problems. Chapter 3 gives tutorials on the construction and use of
spreadsheets. Many other tutorials are included in our supplement, Applications
of Microsoft® Excel in Analytical Chemistry, 2nd ed., and a number of these have
been corrected, updated, and augmented.
• The definitions of molar concentration have been updated in Chapter 4 to
conform to current IUPAC usage, and the associated terminology including
molar concentration and molar analytical concentration have been infused through-
out the text.
• The chapters on statistics (5–7) have been updated and brought into confor-
mity with the terminology of modern statistics. Analysis of variance (ANOVA)
has been included in Chapter 7. ANOVA is very easy to perform with modern
spreadsheet programs and quite useful in analytical problem solving. These chap-
ters are closely linked to our Excel supplement through Examples, Features, and
Summaries.
• In Chapter 8, explanations of external standard, internal standard, and stan-
dard additions methods have been clarified, expanded, and described more
thoroughly. Special attention is paid to the use of least-squares methods in stan-
dardization and calibration.
• A new introduction and explanation of mass balance has been written for
Chapter 11.
• An explanation and a marginal note have been added on the gravimetric factor.
• A new feature on the master equation approach was added to Chapter 14.
• Chapter 17 has been rewritten to include both complexation and precipitation
titrations.
• Chapters 18, 19, 20, and 21 on electrochemical cells and cell potentials have
been revised to clarify and unify the discussion. Chapter 23 has been altered to
decrease the emphasis on classical polarography. The chapter now includes a dis-
cussion of cyclic voltammetry.
• In Chapter 25, the discussion on thermal IR detectors now puts more emphasis
on the DTGS pyroelectric detector.
• Chapter 29 introduces both atomic and molecular mass spectrometry and covers
the similarities and differences in these methods. The introduction of mass spec-
trometry allows the separation chapters (31–34) to place additional emphasis on
combined techniques, such as chromatographic methods with mass spectromet-
ric detection.
• The challenge problems have been updated, augmented, and replaced where
appropriate.
• References to the analytical chemistry literature have been updated and corrected
as necessary.
• Digital Object Identifiers (DOIs) have been added to most references to the primary
literature. These universal identifiers greatly simplify the task of locating articles
by a link on the website www.doi.org. A DOI may be typed into a form on the
home page, and when the identifier is submitted, the browser transfers directly to
the article on the publisher’s website. For example, 10.1351/goldbook.C01222
xvi Preface
can be typed into the form, and the browser is directed to the IUPAC article on
concentration. Alternatively, DOIs may be entered directly into the URL blank
of any browser as http://dx.doi.org/10.1351/goldbook.C01222. Please note that
students or instructors must have authorized access to the publication of interest.
Style and Format. We have continued to make style and format changes to make the
text more readable and student friendly.
• We have attempted to use shorter sentences, a more active voice, and a more
conversational writing style in each chapter.
• More descriptive figure captions are used whenever appropriate to allow a
student to understand the figure and its meaning without alternating between
text and caption.
• Molecular models are used liberally in most chapters to stimulate interest in the
beauty of molecular structures and to reinforce structural concepts and descriptive
chemistry presented in general chemistry and upper-level courses.
• Several new figures have replaced obsolete figures of past editions.
• Photographs, taken specifically for this text, are used whenever appropriate to
illustrate important techniques, apparatus, and operations.
• Marginal notes are used throughout to emphasize recently discussed concepts or
to reinforce key information.
• Key terms are now defined in the margins throughout the book.
• All examples now delineate the question and its answer or solution.
SUPPORTING MATERIALS
Please visit www.cengage.com/chemistry/skoog/fac9 for information about student
and instructor resources for this text.
To get access, visit ACKNOWLEDGMENTS

CengageBrain.com
We wish to acknowledge with thanks the comments and suggestions of many review-
ers who critiqued the eighth edition prior to our writing or who evaluated the current
manuscript in various stages.
REVIEWERS
Lane Baker, Gary Rice,
Indiana University College of William and Mary
Heather Bullen, Kathryn Severin,
Northern Kentucky University Michigan State University
Peter de Boves Harrington, Dana Spence,
Ohio University Michigan State University
Jani Ingram, Scott Waite,
Northern Arizona University University of Nevada, Reno
R. Scott Martin,
St. Louis University
We especially acknowledge the assistance of Professor David Zellmer, California State

University, Fresno, who served as the accuracy reviewer for the book. Dave’s deep
knowledge of analytical chemistry, his tight focus on detail, and his problem-solving
and spreadsheet prowess are powerful assets for our team. We are especially indebted
to the late Bryan Walker, who, while a student in Dave Zellmer’s analytical chemistry
course, gleefully reported a number of errors that Dave (and we) had not detected
Preface xvii
in the eighth edition. Bryan’s pleasant personality, academic talent, and attention to
detail inspired Dave as he worked with us on this edition. We extend a special thanks
to James Edwards of St. Louis University for checking all the back-of-the-book
answers to the Questions and and Problems. We also appreciate the good works of
Professor Bill Vining of the State University of New York, Oneonta, who prepared
many online tutorials and Charles M. Winters, who contributed many of the photos
in the text and most of the color plates.
Our writing team enjoys the services of a superb technical reference librarian, Ms.
Janette Carver of the University of Kentucky Science Library. She assisted us in many
ways in the production of this book, including checking references, performing lit-
erature searches, and arranging for interlibrary loans. We appreciate her competence,
enthusiasm, and good humor.
We are grateful to the many members of the staff of Cengage, who provided solid
support during the production of this text. Acquiring Sponsoring Editor Chris Simp-
son has provided excellent leadership and encouragement throughout the course
of this project. This is our fourth book with Senior Developmental Editor Sandi
Kiselica. As always, she has done a marvelous job of overseeing and organizing the
project, maintaining continuity, and making many important comments and sugges-
tions. Simply put, she’s the best in the business, and we sincerely appreciate her work.
We are grateful to our copy editor, James Corrick, for his consistency and attention
to detail. His keen eye and excellent editorial skills have contributed significantly to
the quality of the text. Alicia Landsberg has done a fine job coordinating the various
ancillary materials, and Jeremy Glover, our photo researcher, has handled the many
tasks associated with acquiring new photos and securing permissions for graphics.
Project Manager Erin Donahue of PreMediaGlobal kept the project moving with
daily reminders and frequent schedule updates while coordinating the entire pro-
duction process. Her counterpart at Cengage was Content Project Manager Jennifer
Risden, who coordinated the editorial process. Finally, we thank Rebecca Berardy
Schwartz, our Cengage media editor for this edition.
This is the first edition of Fundamentals of Analytical Chemistry written without the
skill, guidance, and counsel of our senior coauthors Douglas A. Skoog and Donald
M. West. Doug died in 2008, and Don followed in 2011. Doug was Don’s preceptor
while he was a graduate student at Stanford University, and they began writing ana-
lytical chemistry textbooks together in the 1950s. They produced twenty editions of
three best-selling textbooks over a period of forty-five years. Doug’s vast knowledge of
analytical chemistry and consummate writing skill coupled with Don’s organizational
expertise and attention to detail formed an outstanding complement. We aspire to
maintain the high standard of excellence of Skoog and West as we continue to build
on their legacy. In honor of their manifest contributions to the philosophy, organiza-
tion, and writing of this book and many others, we have chosen to list their names
above the title. Since the publication of the eighth edition, the team lost another part-
ner in Judith B. Skoog, Doug’s wife who died in 2010. Judy was a world-class editorial
assistant who typed and proofread twenty editions of three books (and most of the
instructor’s manuals), amounting to well over 100,000 pages. We miss her accuracy,
speed, tenacity, good humor, and friendship in producing beautiful manuscripts.
Finally, we are deeply grateful to our wives Vicki Holler and Nicky Crouch for
their counsel, patience, and support during the several years of writing this text and
preparing it for production.
F. James Holler
Stanley R. Crouch
The Nature of
Analytical Chemistry CHAPTER 1
A nalytical chemistry is a measurement science consisting of a set of powerful ideas

and methods that are useful in all fields of science, engineering, and medicine. Some
exciting illustrations of the power and significance of analytical chemistry have occurred, are
occurring, and will occur during NASA’s rover explorations of the planet Mars. On July 4, 1997,
the Pathfinder spacecraft delivered the Sojourner rover to the Martian surface. Analytical in-
struments returned information on the chemical composition of rocks and soil. Investigations
by the lander and rover suggested that Mars was at one time in its past warm and wet with
liquid water on the surface and water vapor in the atmosphere. In January 2004, the Mars
rovers Spirit and Opportunity arrived on Mars for a three-month mission. A major result from
Spirit’s alpha particle X-ray spectrometer (APXS) and Mossbauer spectrometer was finding
concentrated deposits of silica and, at a different site, high concentrations of carbonate.
Spirit continued to explore and transmit data until 2010, outliving even the most optimistic
predictions. Even more amazing, Opportunity continues to travel the surface of Mars and, by
March, 2012, had covered more than 21 miles exploring and transmitting images of craters,
small hills, and other features.
In late 2011, the Mars Science Laboratory aboard the rover Curiosity was launched.
It arrived on August 6, 2012 with a host of analytical instruments on board. The Chemis-
try and Camera package includes a laser-induced breakdown spectrometer (LIBS, see
Chapter 28) and a remote microimager. The LIBS instrument will provide determination
NASA/JPL-Caltech
NASA/JPL-Caltech
Mars Science Laboratory aboard rover Curiosity Curiosity observing Martian landscape from Gale crater, August 2012
2 CHAPTER 1 The Nature of Analytical Chemistry
of many elements with no sample preparation. It can determine the identity and amounts
of major, minor, and trace elements and can detect hydrated minerals. The sample analy-
sis package contains a quadrupole mass spectrometer (Chapter 29), a gas chromatograph
(Chapter 32), and a tunable laser spectrometer (Chapter 25). Its goals are to survey carbon
compound sources, search for organic compounds important to life, reveal the chemical and
isotopic states of several elements, determine the composition of the Martian atmosphere,
and search for noble gas and light element isotopes.1
These examples demonstrate that both qualitative and quantitative information are
Qualitative analysis reveals the iden- required in an analysis. Qualitative analysis establishes the chemical identity of the
tity of the elements and compounds in species in the sample. Quantitative analysis determines the relative amounts of these
a sample.
species, or analytes, in numerical terms. The data from the various spectrometers on
Quantitative analysis indicates the the rovers contain both types of information. As is common with many analytical instru-
amount of each substance in a sample.
ments, the gas chromatograph and mass spectrometer incorporate a separation step as
Analytes are the components of a a necessary part of the analytical process. With a few analytical tools, exemplified here
sample that are determined.
by the APXS and LIBS experiments, chemical separation of the various elements con-
tained in the rocks is unnecessary since the methods provide highly selective informa-
tion. In this text, we will explore quantitative methods of analysis, separation methods,
and the principles behind their operation. A qualitative analysis is often an integral part
of the separation step, and determining the identity of the analytes is an essential ad-
junct to quantitative analysis.
1A The Role of Analytical Chemistry

Analytical chemistry is applied throughout industry, medicine, and all the sci-
ences. To illustrate, consider a few examples. The concentrations of oxygen and
of carbon dioxide are determined in millions of blood samples every day and
used to diagnose and treat illnesses. Quantities of hydrocarbons, nitrogen oxides,
and carbon monoxide present in automobile exhaust gases are measured to deter-
mine the effectiveness of emission-control devices. Quantitative measurements
of ionized calcium in blood serum help diagnose parathyroid disease in humans.
Quantitative determination of nitrogen in foods establishes their protein content
and thus their nutritional value. Analysis of steel during its production permits
adjustment in the concentrations of such elements as carbon, nickel, and chro-
mium to achieve a desired strength, hardness, corrosion resistance, and ductility.
The mercaptan content of household gas supplies is monitored continually to
ensure that the gas has a sufficiently obnoxious odor to warn of dangerous leaks.
Farmers tailor fertilization and irrigation schedules to meet changing plant needs
during the growing season, gauging these needs from quantitative analyses of
plants and soil.
Quantitative analytical measurements also play a vital role in many research
areas in chemistry, biochemistry, biology, geology, physics, and the other sci-
ences. For example, quantitative measurements of potassium, calcium, and
sodium ions in the body fluids of animals permit physiologists to study the role
these ions play in nerve-signal conduction as well as muscle contraction and re-
laxation. Chemists unravel the mechanisms of chemical reactions through reac-
tion rate studies. The rate of consumption of reactants or formation of products
1
For details on the Mars Science Laboratory mission and the rover Curiosity, see http://www.nasa.gov.
1A The Role of Analytical Chemistry 3
in a chemical reaction can be calculated from quantitative measurements made

at precise time intervals. Materials scientists rely heavily on quantitative analyses
of crystalline germanium and silicon in their studies of semiconductor devices
whose impurities lie in the concentration range of 1 3 1026 to 1 3 1029 per-
cent. Archaeologists identify the sources of volcanic glasses (obsidian) by measur-
ing concentrations of minor elements in samples taken from various locations.
This knowledge in turn makes it possible to trace prehistoric trade routes for
tools and weapons fashioned from obsidian.
Many chemists, biochemists, and medicinal chemists devote much time in
the laboratory gathering quantitative information about systems that are im-
portant and interesting to them. The central role of analytical chemistry in
this enterprise and many others is illustrated in Figure 1-1. All branches of
chemistry draw on the ideas and techniques of analytical chemistry. Analyti-
cal chemistry has a similar function with respect to the many other scientific
fields listed in the diagram. Chemistry is often called the central science; its top
center position and the central position of analytical chemistry in the figure
Chemistry
Biochemistry
Inorganic Chemistry
Biology Organic Chemistry
Botany Physical Chemistry Physics
Genetics Astrophysics
Microbiology Astronomy
Molecular Biology Biophysics
Zoology
Geology Engineering
Geophysics Civil
Geochemistry Chemical
Paleontology Electrical
Paleobiology Mechanical
Analytical
Chemistry
Environmental Medicine
Sciences Clinical Chemistry
Ecology Medicinal Chemistry
Meteorology Pharmacy
Oceanography Toxicology
Agriculture
Agronomy Materials Science
Animal Science Metallurgy
Crop Science Polymers
Food Science Solid State
Social Sciences
Horticulture
Archeology
Soil Science
Anthropology
Forensics
Figure 1-1 The relationship between analytical chemistry, other branches of chemistry,
and the other sciences. The central location of analytical chemistry in the diagram signifies its
importance and the breadth of its interactions with many other disciplines.
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CHAPTER III.
WILDSHOTT
Wildshott, the Hampshire seat of the Kennetts, stands off the

Winton-Sarum road, at a distance of some six miles from the former,
and some three and a half from the sporting town of Longbridge, on
the way to the latter. The house is lonely situated in wild but beautiful
country, lying as it does in the trough of the great downs whose
summits hereabouts command some of the most spacious views in
the County. A mile north-east, footing a gentle incline, shelters the
village of Leighway; less than a mile away, in a hollow of the main
road, stands a wayside tavern called the Bit and Halter; and, with
these two exceptions, no nearer neighbour has Wildshott than the
tiny Red Deer inn, which perches on a high lift of the downs a mile
and a half distant, rising north.
The stately, wrought-iron gates of Wildshott open from the main
road. Thence a drive of considerable extent reaches to the house,
which is a rectangular red-brick Jacobean structure, with stone
string-courses and a fine porch, having a great shell over it. There
are good stables contiguous, and the grounds about are ample and
well timbered—almost too well timbered, it might be thought by some
people, since the closeness of the foliage gives an effect of gloom
and solemnity to a building which, amid freer surroundings, should
have nothing but grace and frankness to recommend it. But settled
as it is in the wash of the hills, with their moisture draining down
upon it, growth and greenness have become a tradition of its life,
and as such not to be irreverently handled by succeeding
generations of Kennetts.
All down the west boundary of the upper estate—which, to its
northernmost limit, breaks upon that bare hill on whose summit, at
closer range now, the little Red Deer inn sits solitary—runs a wide
fringe of beech-wood, which is continued to the high road, and
thence, on the further side, dispersed among the miscellaneous
plantations which are there situated. The highway itself roughly
bisects the property—the best of whose grass and arable lands are
contained in the southern division—and can be reached from the
house, if one likes, through the long beech thicket by way of a
narrow path, which, entering near the stables, runs as far as the
containing hedge, in which, at some fifty yards from the main
entrance, is a private wicket, leading down by a couple of steps to
the road. This path is known, through some superstitious
association, as the Bishop’s Walk, and is little used at any time, the
fact that it offers a short cut from the house to the lower estate being
regarded, perhaps, as inadequate compensation for its solitariness,
its dankness, and the glooms of the packed foliage through which it
penetrates. Opposite the wicket, across the road, an ordinary bar-
gate gives upon a corresponding track, driven through the thick of a
dense coppice, which, at a depth of some two hundred feet, ends in
the open fields. It is useful to bear in mind these local features, in
view of the event which came presently to give them a tragic
notoriety.
At Winton a wagonette met the two gentlemen, and they were
landed at Wildshott soon after four o’clock. Bickerdike was interested
to discover that they were the only guests. He was not surprised for
himself, since he and Hugo Kennett were on terms of unceremonial
intimacy. He did wonder a little what qualities he and the Baron could
be thought to possess in common that they should have been
chosen together for so exclusive an invitation. But no doubt it was
pure accident; and in any case there was his friend to explain. He
was a bit down in the mouth, was Hugo—for any reason, or no
reason, or the devil of a reason; never mind what—and old Viv was
always a tower of strength to him in his moods—hence old Viv’s
citation to come and “buck” his friend, and incidentally to enjoy a few
days’ shooting, which accounted for one half of the coincidence. Old
Viv accepted his part philosophically; it was not the first time he had
been called upon to play it with this up and down young officer,
whose temporal senior he was by some six years, and whose elder,
in all questions of sapience and self-sufficiency, he might have been
by fifty. He did not ask what was the matter, but he said “all right,” as
if all right were all reassurance, and gave a little nod to settle the
matter. He had a well-looking, rather judicial face, clean shaven, a
prim mouth, a somewhat naked head for a man of thirty, and he wore
eyeglasses on a neatly turned nose, with a considerable prominence
of the organ of eventuality above it. The complacent bachelor was
writ plain in his every line. And then he inquired regarding the Baron.
“O! I know very little about him,” was young Kennett’s answer. “I
believe the governor picked him up in Paris originally, but how or
where I can’t say. He’s a marvel at chess; and you remember that’s
the old man’s obsession. They’re at it eternally while he’s down
here.”
“This isn’t his first visit then?”
“No, I believe not; but it’s the first time I’ve seen him. I’m quoting
Audrey for the chess. Why, what’s the matter? Is anything wrong with
him?”
“There you go, you rabbit! Who said anything was wrong with him?
I’ve met him before, that’s all.”
“Have you? Where?”
“Why, in Paris. You remember the Montesquieu, and my French
Baron?”
“I remember there was a Baron. I don’t think you ever told me his
name.”
“Well, it was Le Sage, and this is the man.”
“Is it? That’s rather queer.”
“What is?”
“The coincidence of your meeting again like this.”
“O, as to that, coincidence, you know, is only queer till you have
traced back its clues and found it inevitable.”
“Well, that’s true. You can trace it in his case to the governor’s
being down with the gout again, and confined to the house, and
wanting something and somebody to distract him.”
“There you are, you see. He thought of chess, and thought of this
Le Sage, and wrote up to him on the chance. Your father probably
knows more about his movements than we do. So we’re both
accounted for. No, what is queer to me is the man’s confounded
habit of secrecy. Why didn’t he say, when I met him in Paris, that the
friend I was waiting for was known to him? Why didn’t he admit
yesterday, admit until we actually met on the platform to-day, that we
were bound for the same place? I hate a stupidly reticent man.”
Kennett laughed, and then frowned, and turned away to chalk his
cue. The two men were in the billiard-room, playing a hundred up
before dinner.
“Well,” he said, stooping to a losing hazard, “I hope a fellow may
be a good fellow, and yet not tell all that’s in him.”
“Of course he may,” answered Bickerdike. “Le Sage, I’m sure, is a
very good fellow, a very decent old boy, and rare company when he
chooses—I can answer for that. But there’s a difference between
telling all that’s in one and not telling anything.”
“Well, perhaps he thinks,” said the other impatiently, “that if he
once opened the sluice he’d drain the dammed river. Do let him
alone and attend to the game.”
Bickerdike responded, unruffled. He had found his friend in a
curiously touchy state—irritable, and nervous, and moody. He had
known him to be so before, though never, perhaps, so
conspicuously. Hugo was temperamentally high-strung, and always
subject to alternations of excitement and despondence; but he had
not yet exhibited so unbalanced a temper as he seemed inclined to
display on this occasion. He was wild, reckless, dejected, but seldom
normal, appearing possessed by a spirit which in turns exalted or
depressed him. What was wrong with the boy? His friend, covertly
pondering the handsome young figure, found sufficient solution in
the commonplace. He was in one of his nervous phases, that was
all. They would afflict men subject to them at any odd time, and
without apparent provocation. It was one of the mysteries of our
organic being—a question of misfit somewhere between spirit and
matter. No one looking at the young soldier would have thought him
anything but a typical example of his kind—constitutionally flawless,
mentally insensitive. He belonged to a crack regiment, and was
popular in it; was tall, shapely-built, attractive, with a rather girlish
complexion and umber-gold hair—a ladies’ man, a pattern military
man, everything nice. And yet that demon of nerve worked in him to
his perfection’s undoing. Perhaps it was the prick of conscience, like
a shifting grit in one’s shoe, now here, now there, now gone—for the
boy had quite fine impulses for a spoilt boy, a spoilt child of Fortune
—and spoilt, like Byron by his mother, in the ruinous way. His father,
the General, alternately indulgent and tyrannical, was the worst of
parents for him; he had lost his mother long ago; his one sister,
flippant, independent—undervalued, it may be, and conscious of it—
offered no adequate substitute for that departed influence. And so
the good in Hugo was to his own credit, and stood perhaps for more
than it might have in another man.
His father, Sir Calvin—he had got his K.C.B., by the way, after Tel-
el-Kebir in ’82, in reward for some signal feat of arms, and at the
expense of his trigger-finger—was as proud as sin of his comely lad,
and blind to all faults in him which did not turn upon opposition to
himself. He designed great connexions for the young man, and
humoured his own selfishness in the prospect. He was a martinet of
fifty-five, with a fine surface polish and a heart of teak beneath it, a
patrician of the Claudian breed, irascible, much subject to gout for
his past misdeeds, and an ardent devotee of the game of chess, at
which he could hold his own with some of the professed masters. It
was that devotion which had brought him fortuitously acquainted with
the French Baron—a sort of technical friendship, it might be called—
and which had procured the latter an occasional invitation of late to
Wildshott. Le Sage came for chess, but he proved very welcome for
himself. There was a sort of soothing tolerance about him, the well-
informed urbanity of a polished man of the world, which was as good
as a lenitive to the splenetic invalid. But nobody, unless it were Sir
Calvin himself, appeared to know anything concerning him; whether
he were rich or indigent; what, if dependent on his wits, he did for a
living; what was the meaning or value of his title in an Englishman, if
English he were; whether, in short, he were a shady Baron of the
chevalier d’industrie order, or a reputable Baron, with only some
eccentricities to mark him out from the common. One of these, not
necessarily questionable, was his sly incommunicativeness; another
was his fondness for half-crowns. He invariably, whether with Sir
Calvin or others, made that stake, no more and no less, a condition
of his playing at all, and for the most part he carried it off. Vivian
Bickerdike soon learned all that there was to be told about him, and
he was puzzled and interested—“intrigued,” as they would say in the
horrible modern phrase. But being a young man of caution, in
addition to great native curiosity, he kept his wits active, and his
suspicions, if he had any, close.
The game proceeded—badly enough on the part of Hugo, who
was generally a skilful player. He fouled or missed so many shots
that his form presently became a scandal. “Phew!” whistled his
opponent, after a peculiarly villainous attempt; “what’s gone wrong
with you?”
The young man laughed vexedly; then, in a sudden transition to
violence, threw his cue from him so that it clattered on the floor.
“I can’t play for nuts,” he said. “You must get somebody else.”
“Hugh,” said his friend, after a moment or two of silence, “there’s
something weighing on your mind.”
“Is there?” cried the other jeeringly. “I wonder.”
“What is it? You needn’t tell me.”
“O! thank you for that. I tell you what, Viv: I dreamed last night I
was sitting on a barrel of gunpowder and smoking a cigarette, and
the sparks dropped all about. Didn’t I? That’s what I feel, anyhow.
Nerves, all nerves, my boy. O! shut up that long mug, and talk of
something else. I told you I was off colour when I wrote.”
“I know you did, and I came down.”
“Good man. You’ll be in at the kill. There’s going to be a most
infernal explosion—pyrotechnics galore. Or isn’t there? Never mind.”
He appeared to Bickerdike to be in an extraordinary state, verging
on the hysterical. But no more was said, and in a few moments they
parted to dress for dinner.
M. le Baron, coming up to his room about the same time and for
the same purpose, was witness of a little stage comedy, which, being
for all his bulk a light treader, he surprised. The actors were his valet
Louis and an under-housemaid, the latter of whom was at the
moment depositing a can of hot water in the washing basin. He saw
the lithe, susceptible little Gascon steal from his task of laying ready
his master’s dress clothes, saw him stalk his quarry like a cat,
pounce, enfold the jimp waist, heard the startled squeal that
followed, a smack like a hundred kisses, a spitting sacré chien! from
the discomfited assailant, as he staggered back with a face of fury
and a hand held to his ear, and, seeing, stood to await the upshot, a
questioning smile upon his lips. Both parties realised his presence at
the same instant, and checked the issue of hot words which was
beginning to join between them. The girl, giving a defiant toss to her
chin, hurried past Le Sage and out of the room; M. Louis Cabanis
returned to his business with the expression of a robbed wild-cat.
Le Sage said nothing until he was being presently helped on with
his coat, and then suddenly challenging the valet, eye to eye, he
nodded, and congratulated him:—
“That is better, my friend. It is not logical, you know, for the injurer
to nurse the grievance.”
The Gascon looked at his master gravely.
“Will you tell me who is the injurer, Monsieur?”
“Surely,” answered Le Sage, “it cannot be she, in these first few
hours of your acquaintance?”
“But if she had appeared to encourage me, Monsieur?”
The Baron laughed.
“The only appearance to be trusted in a pretty woman, Louis, is
her prettiness.”
“Monsieur, is her ravishing loveliness.”
“Well, well, Louis, as you will. Only bear it no grudge.”
He turned away from a parting keen scrutiny of the dark,
handsome face, and left the room, softly carolling. The little episode
had amused rather than surprised him. Certainly it had seemed to
point, in respect of time, to a quite record enslavement on the
Gascon’s part; but then the provocation to that passionate
impressionable nature! For the girl had been really amazingly pretty,
with that cast of feature, that Hebe-like beauty of hair and eye and
complexion about whose fascination no two properly constituted
minds could disagree. She was a domestic servant—and she was a
young morning goddess, fresh from the unsullied dawn of Nature, a
Psyche, a butterfly, a Cressid like enough. “If I were younger,”
thought Le Sage, “even I!” and he carolled as he went down to
dinner.
CHAPTER IV.
I AM INTERESTED IN THE BARON
(From the Bickerdike MS.)

I seemed conscious somehow, at dinner on the night of our arrival, of
a feeling of electricity in the domestic atmosphere. Having no clue,
such as the later course of events came to supply, to its origin, I
diagnosed it, simply and vulgarly, as the vibrations from a family jar,
of the sort to which even the most dignified and well-regulated
households cannot always rise superior. Sir Calvin himself, exacting
and domineering, could never at the best of times be considered a
tactful autocrat: a prey to his hereditary foe, he appeared often to go
out of his way to be thought detestable. When such was the case,
his habit of harping on grievances could become an exquisite torture,
his propensity for persisting in the unwelcome the more he saw it
resented a pure malignancy. On this occasion, observing an obvious
inclination in his son, my friend, to silence and self-obliteration, he
took pleasure in drawing him out, with something of the savagery, I
could not but think, of a fisherman who wrenches an obstinate hermit
crab from its borrowed shell for bait. I saw how poor Hugh was
rasped and goaded, but could do no more than take upon myself,
where I could, the burden of response. Believing at the time that this
aggravated fencing between the two was a part, or consequence, of
some trouble, the serious nature of which might or might not have
been implied in my friend’s recent outburst, I made and could make
but an inefficient second; yet, even had I known, as I came to know,
that my surmise was wrong, and that the father’s persistence was
due to nothing but a perverse devil of teasing, it is not clear to me
how else I could have helped the situation. I could not have hauled
my host by the ears, as I should have liked to do, over his own
dining-room table.
But the sense of atmospheric friction was not confined to these
two. In some extraordinary way it communicated itself to the
servants, the very butler, our young hostess. I had not seen Audrey
at tea, and now greeted her for the first time. She came in late, to
find us, by the Bashaw’s directions, already seated, and to suffer a
sharp reprimand for her unpunctuality which brought a flush to her
young rebellious cheek. Nor did I better things, so far as she was
concerned, by an ostentatious display of attentions; she seemed to
resent my sympathy even more than the harshness which had
provoked it. It is the way of cats and women to tear the hand that
would release them from the trap.
The dinner, in short, began very uncomfortably, with an irascible
host, a moody son, and an offended daughter, the butler taking his
cue from his master, and the servants from the butler. They waited
nervously, and got in one another’s way, only the more flurriedly for
their whispered harrying by the exacerbated Cleghorn. I was
surprised, I confess, by the change in that usually immaculate
dignitary. The very type and pattern of his kind, correct,
imperturbable, pontifical, I had never before known Cleghorn to
manifest the least sign of human emotion, unless it were when Mr.
Yockney, the curate from Leighway, had mixed water with his
Château Margaux 1907. Now, preposterous as it appeared, I could
have believed the great man had been crying. His globous eyes, his
mottled cheeks, bore suspicious evidences of the fact; his very side-
whiskers looked limp. Surely the domestic storm, if such, which had
rocked the house of Kennett must have been demoralising to a
hitherto unknown degree.
It was the Baron who redeemed the situation, winning harmony
out of discord. He had, to do him justice, the reconciliatory faculty,
chiefly, I think, because he could always find, as one should, a bright
interest in differences of opinion instead of a subject for contention. I
never knew him, then or thereafter, to be ruffled by opposition or
contradiction. He accepted them placidly, as constituting possible
rectifications of his own argumentative frontiers.
His opportunity came with a growl of Sir Calvin’s over the lateness
of the evening papers. The General had been particularly curious to
hear the result of a local trial, known as the Antonferry Bank robbery
case, which was just reaching its conclusion, and it chafed him to be
kept waiting. Le Sage asked for information, and the supplying it
smoothed the troubled waters. There is a relish for most people in
being the first to announce news, whether good, bad, or indifferent.
The case, as stated, was remarkable for nothing but the skill with
which it had been unravelled. A Bank in Antonferry—a considerable
market town lying some eight or nine miles north of Wildshott—had
been robbed, and the question was by whom. That question had
been answered in the upshot by an astute Scotland Yard detective,
who, in spite of the obloquy thrown upon his kind by Mr. Sherlock
Holmes, had shown considerable sagacity in tracing the crime to its
source in the Bank’s own manager—a startling dénouement. The
accused, on the strength of this expert’s evidence, had been
committed to stand his trial at Winton Quarter Sessions, and it was
the issue of that event which was interesting Sir Calvin. He had had
some dealings with the Bank in question, and had even been
brought into some personal contact with the delinquent official.
“It seems,” he ended, “that there can be no doubt about the
verdict. That Ridgway is a clever dog.”
“The detective?” queried Le Sage; and the General nodded.
“The sort I should be sorry, if a thief, to have laid on my trail.”
“But supposing you left none?” questioned the Baron, with a smile.
“Ah!” said Sir Calvin, having nothing better to reply.
“I have often thought,” said Le Sage, “that if crime realised its own
opportunities, there would be no use for detectives at all.”
“Eh? Why not?” asked his host.
“Because there would be nothing to find out,” answered the Baron.
“How d’ye mean? Nothing to find out?”
“Nothing whatever. My idea, now, of a successful crime is not a
crime which baffles its investigators, but a crime which does not
appear as a crime at all.”
“Instance, M. le Baron,” I ventured to put in.
“Why,” said Le Sage good-humouredly, “a dozen may well present
themselves to a man of average inventive intelligence. Direct
murder, for example—how crude! when a hundred means offer
themselves for procuring plausible ends to life. Tetanus germs and
an iron tack; ptomaine, that toxicologic mystery, so easy to introduce;
the edge of a cliff and a windy day; a frayed picture cord; a loosened
nut or two; a scrap of soap left on the boards by an opened window
—given adroitness, timeliness, a little nerve, would not any of these
do?”
Audrey drew back in her chair, with a flushed little laugh.
“What a diabolical list!” she said, and made a face as if she had
taken medicine.
“Yes,” said I. “But after all, Baron, this is no more than
generalising.”
“You want a concrete instance?” he answered, beaming on me.
“What do you say then to a swimmer being awarded the Humane
Society’s certificate for attempting to save the life of a man whom he
had really drowned? It needs only a little imagination to fill in the
details.”
“That is good,” I admitted. “We put one to your credit.”
“Again,” said the Baron, “I offer the case of a senseless young
spendthrift. He gambles, he drinks, his life is a bad life from the
insurance company’s point of view. When hard pressed, he is lavish
with his I.O.U.’s; when flush of money he redeems them; he pays up,
he throws the slips into the fire with hardly a glance at them. One
who holds a good deal of his paper observes this, and acts
accordingly. He preserves the original securities, and on redemption,
offers forgeries in their place, which he is careful to see destroyed.
On the death of the young man he puts in his claim on his estate on
the strength of the indisputable original documents. Thus he is paid
twice over, without a possibility of any suspicion arising.”
“But one of the forged I.O.U.’s,” said Audrey, “had been carried up
the chimney without catching a light, and had been blown through
the open window of the young man’s family lawyer, who had kept it
as a surprise.”
There was a shout of laughter, in which the Baron joined.
“Bravo, Audrey!” cried her brother. “What about your average
inventive intelligence, Baron?”
“I said, specifically, a man’s,” pleaded Le Sage. “Women,
fortunately for us, are not eligible for the detective force.”
Audrey laughed at the compliment, but I think she liked the Baron
for his pleasant good-nature. About that, for my part, I kept an open
mind. Had he really invented these cases on the spur of the moment,
or could it be possible that they touched on some experience of his
own? One could not say, of course; but one could bear the point in
mind.
The dinner went cheerfully enough after this jeu d’esprit of
Audrey’s. That had even roused Hugh from his glooms, and to quite
exaggerated effect. He became suddenly talkative where he had
been taciturn, and almost boisterously communicative where he had
been reserved. But I noticed that he drank a good deal, and detected
curiously, as I thought, a hint of desperation under his feverish
gaiety.
In all this, it may be said, I was appropriating to myself, without
authority, a sort of watching brief on behalf of a purely chimerical
client. I had no real justification for suspecting the Baron, either on
his own account, or in association with my friend’s apparent state; it
was presumptive that Sir Calvin knew at least as much about the
man as I did; still, I thought, so long as I preserved my attitude of
what I may call sympathetic vigilance à la sourdine, nothing could be
lost, and something even might be gained. The common
atmosphere, perhaps, affected me with the others, and inclined me
to an unusually observant mood; a mood, it may be, prone to attach
an over-importance to trifles. Thus, I could find food for it in an
incident so ordinary as the following. There was a certain picture on
the wall, a genre painting, to which Le Sage, sitting opposite it,
referred in some connexion. Sir Calvin, replying, remarked that so-
and-so had declared one of the figures to be out of proportion—too
short or too tall, I forget which—and, in order to measure the
discrepancy, interposed, after the manner of the connoisseur, a
finger between his eye and the subject. There was nothing out of the
common in the action, save only that the finger he raised was the
second finger of his right hand, the first having been shot away in
some long-past engagement; but it appeared, quite obviously to me,
to arrest in a curious way the attention of the visitor. He forgot what
he was saying at the moment, his speech tailed off, he sat gazing, as
if suddenly fascinated, not at the picture but at the finger. The next
instant he had caught up and continued what he was observing; but
the minute incident left me wondering. It had signified, I was sure, no
sudden realization of the disfigurement, since that must have been
long known to him, but of some association with it accidentally
suggested. That, in that single moment, was my very definite
impression—I could hardly have explained why at the time; but there
it was. And I may say now, in my own justification, that my instinct, or
my intuition, was not at fault.
Once or twice later I seemed to catch Le Sage manœuvring to
procure a repetition of the action, but without full success; and soon
afterwards the two men fell upon the ever-absorbing subject of
chess, and lapsed into vigorous discussion over the relative merits of
certain openings, such as the Scotch, the Giuoco Piano, the Ruy
Lopez attack, Philidor’s defence, and the various gambits; to wit, the
Queen’s, the Allgaier, the Evans, the Muzio, the Sicilian, and God
knows what else. They did not favour the drawing-room for long after
dinner, but went off to the library to put their theories into practice,
leaving Hugh and me alone with the lady. I cannot admit that I found
the subsequent evening exhilarating. Hugh appeared already to be
suffering a relapse from his artificial high spirits, and again disturbed
me by the capricious oddity of his behaviour. He and his sister
bickered, after their wont, a good deal, and once or twice the girl was
brought by him near the verge of angry tears, I thought. I never could
quite make out Audrey. She seemed to me a young woman of good
impulses, but one who was for ever on the defensive against
imagined criticism, and inclined therefore, in a spirit of pure
perversity, to turn her worst side outermost. Yet she was a really
pretty girl, a tall stalk of maidenhood, nineteen, and athletically
modern in the taking sense, and had no reason but to value herself
and her attractions at the plain truth they represented. The trouble
was that she was underestimated, and I think proudly conscious of
the fact. With a father like Sir Calvin, it was, and must be, Hugo first
and the rest nowhere. He bullied every one, but there was no under-
suggestion of jealous proprietorship in his bullying of Audrey as there
was in his adoring bullying of his son. He did not care whether she
felt it or not; with the other it was like a lover’s temper, wooing by
chastisement. Nor was Hugo, perhaps, a very sympathetic brother.
He could enjoy teasing, like his father, and feel a mischievous
pleasure in seeing “the galled jade wince.” Audrey, I believe, would
have worshipped him had he let her—I had observed how gratified
she looked at dinner over his commendation of her jest—but he held
her aloof between condescension and contempt, and the two had
never been real companions. The long-motherless girl was lonely, I
think, and it was rather pathetic; still, she did not always go the right
way about it to avoid unfavourable criticism.
We were out for a day in the stubble on the morrow, and I made it
an excuse for going to bed betimes. The trial of the Bank-Manager, I
may mention by the way, had ended in a verdict of guilty, and a
sentence of three years penal servitude. I found, and took the paper
in to Sir Calvin before going upstairs. The servants never dared to
disturb him at his game.
CHAPTER V.
THE BARON CONTINUES TO INTEREST ME
(From the Bickerdike MS.)

We were three guns—Hugo, myself, and a young local landowner,
Sir Francis Orsden, of Audley, whom I had met before and liked. He
was a good fellow, though considered effeminate by a sporting
squirearchy; but that I could never see. Our shooting lay over the
lower estate, from which the harvest had lately been carried, and we
went out by the main gates, meeting the head gamekeeper, Hanson,
with the dogs and a couple of boy beaters, in the road. Our plan was
to work the stubble as far as possible in a south-westerly direction,
making for Asholt Copse and Hanson’s cottage, where Audrey and
the Baron were to meet us, driving over in a pony trap with the lunch.
I perceived early enough that my chance of a day’s sport wholly
untrammelled by scruples of anxiety was destined to be a remote
one. Hugh, it had been plain to me from the first, had not mastered
with the new day his mood of the night before. His nervous irritability
seemed to me even to have increased, and the truth was he was a
trying companion. I had already made him some tentative bid for his
confidence, but without result; I would not be the one again to proffer
my sympathy uninvited. After all, he had asked for it, and was the
one to broach the subject, if he wanted it broached. Probably—I
knew him—the matter was no great matter—some disappointment or
monetary difficulty which his fancy exaggerated. He hated trouble of
any sort, and was quite capable of summoning a friend from a sick-
bed to salve some petty grievance for him. So I left to him to explain,
if and when he should think proper.
It was a grey quiet day, chill, but without wind; the sort of day on
which the echo of a shot might sound pretty deceptively from a
distance—a point to be remembered. I was stationed on the left,
Orsden on the extreme right, and Hugh divided us. His shooting was
wild to a degree; he appeared to fire into the thick of the coveys
without aim or judgment, and hardly a bird fell to his gun. Hanson,
who kept close behind his young master, turned to me once or twice,
when the lie of the ground brought us adjacent, and shook his head
in a surprised, mournful way. Once Hugh and I came together at a
gap in a hedge. I had negotiated it without difficulty, and my friend
was following, when something caught my eye. I snatched at his gun
barrel, directing it between us, and on the instant the charge
exploded.
“Good God, man!” I exclaimed. “You?”
Like the veriest Cockney greenhorn, he had been pulling his piece
after him by the muzzle, and the almost certain consequence had
followed. I stood staring at him palely, and for the moment his face
was distorted.
“Hugh!” I said stiffly, “you didn’t mean it?”
He broke into a mirthless laugh.
“Mean it, you mug! Of course I didn’t mean it. Why should I?”
“I don’t know. Mug for saving your life, anyhow!”
“I’ll remember it, Vivian. I wish I owed you something better worth
the paying.”
“That’s infernal nonsense, of course. Now, look here; what’s it all
about?”
“All what?”
“You know.”
“I’ll tell you by-and-by, Viv—on my honour, I will.”
“Will you? Hadn’t you better go back in the meantime and leave
your gun with Hanson?”
“No; don’t be a fool, or make me seem one. I’ll go more careful
after this; I promise you on my sacred word I will. There, get on.”
I was not satisfied; but Hanson coming up at the moment to see
what the shot had meant, I could have no more to say, and prepared
silently to resume my place.
“It’s all right, George,” said his master, “only a snap at a rabbit.”
Had he meant to kill himself? If he had, what trouble so much
more tragic than any I had conceived must lie at the root of the
matter! But I would not dare to believe it; it had been merely another
manifestation of the reckless mood to which his spoilt temper could
only too easily succumb. Nevertheless, I felt agitated and disturbed,
and still, in spite of his promise, apprehensive of some ugly
business.
He shot better after this episode, however, and thereby brought
some reassurance to my mind. Hanson, that astute gamekeeper, led
us well and profitably, and the morning reached its grateful end in
that worthy’s little parlour in the cottage in the copse, with its cases
of stuffed birds and vermin, and its table delectably laid with such
appetising provender as ham, tongue, and a noble pigeon pie, with
bottled beer, syphons, and old whisky to supply the welcome
moisture. Audrey presided, and the Baron, who had somehow won
her liking, and whom she had brought with her in the governess cart,
made a cheerful addition to the company. He was brightly interested
in our morning’s sport, as he seemed to be generally in anything and
everything; but even here one could never make out from his
manner whether his questions arose from knowledge or ignorance in
essential matters. They were not, I suppose—in conformity with his
principle of inwardness—intended to betray; but the whole thing was
to my mind ridiculous, like rattling the coppers in one’s pocket to
affect affluence. One might have gathered, for all proof to the
contrary, that his acquaintance with modern sporting weapons was
expert; yet he never directly admitted that he had used them, or was
to be drawn into any relation of his personal experiences in their
connexion. The subject of poachers was one on which, I remember,
he exhibited a particular curiosity, asking many questions as to their
methods, habits, and the measures taken to counter their dangerous
activities. It was Orsden who mostly answered him, in that high
eager voice of his, with just the suspicion of a stammer in it, which I
could never hear without somehow being tickled. Hugh took no
trouble to appear interested in the matter. He was again, I noticed
with uneasiness, preoccupied with his own moody reflections, and
was drinking far too much whisky and soda.
The Baron asked as if for information; yet it struck me that his
inquiries often suggested the knowledge they purported to seek, as
thus:—
“Might it not be possible, now, that among the quiet, respectable
men of the village, who attend to their business, drink in moderation,
go punctually to church, and are well thought of by the local
policeman, the real expert poacher is mostly to be found—the man
who makes a study and a business of his craft, and whose
depredations, conducted on scientific and meteorological lines,
should cause far more steady havoc among the preserves than that
wrought by the organised gangs, or by the unprofessional loafer
—‘moucher,’ I think you call him?”
Or thus: “This country now, with its mixture of downlands and low
woods, and the variety of opportunities they afford, should be, one
might imagine, peculiarly suited to the operations of these gentry?”
Or thus: “I wonder if your shrewd poacher makes much use of a
gun, unless perhaps on a foggy morning, when the sound of the
report would be muffled? He should be a trapper, I think, par
excellence”—and other proffered hypotheses, seeming to show an
even more intimate acquaintance with the minutiæ of the subject,
such as the springes, nets, ferrets, and tricks of snaring common to
the trade—a list which set Orsden cackling after a time.
“On my word, Baron,” said he, “if it wasn’t for your innocent way of
p-putting things, I could almost suspect you of being a poacher
yourself.”
Le Sage laughed.
“Of other men’s game, in books, perhaps,” he said.
“Well,” said Orsden, “you’re right so far, that one of the closest and
cunningest poachers I ever heard of was a Leighway hedge-
carpenter called Cleaver, and he was as quiet, sober, civil-spoken a
chap as one could meet; pious, too, and reasonable, though a bit of
a village politician, with views of his own on labour. Yet it came out
that for years he’d been making quite a handsome income out of
Audley and its neighbours—a sort of D-Deacon Brodie, you know.
Not one of their preserves, though; you’re at fault there, Baron. Your
local man knows better than to put his head into the noose. His
dealings are with the casual outsiders, so far as pheasants are
concerned. When he takes a gun, it’s mostly to the birds; and of
course he shoots them sitting.”
“Brute!” said Audrey.
“Well, I don’t know,” said the young Baronet. “He’s a tradesman,
isn’t he, not a sportsman, and tradesmen don’t give law.”
“How did he escape so long?” asked the girl.
“Why, you see,” answered Orsden, “you can’t arrest a man on
suspicion of game-stealing with nothing about him to prove it. He
must be caught in the act; and if one-third of his business lies in
poaching, quite two-thirds lie in the art of avoiding suspicion. Fellows
like Cleaver are cleverer hypocrites than they are trappers—J-
Joseph Surfaces in corduroys.”
“Do you find,” said Le Sage, “men of his kind much prone to
violence?”
“Not usually,” replied Orsden, “but they may be on occasion, if
suddenly discovered at work with a gun in their hands. It’s exposure
or murder then, you see; ruin or safety, with no known reason for any
one suspecting them. I expect many poor innocent d-devils were
hanged in the old days for the sins of such vermin.”
“Yes,” said Le Sage, “a shot-gun can be a great riddler.”
One or two of us cackled dutifully over the jeu de mot. Could we
have guessed what tragic application it would receive before the day
was out, we might have appreciated it better, perhaps.
I shall not soon forget that afternoon. It began with Audrey and the
Baron driving off together for a jaunt in the little cart. They were very
merry, and our young Baronet would have liked, I think, to join them.
I had noticed Le Sage looking excessively sly during lunch over what
he thought, no doubt, was an exclusive discovery of his regarding
these two. But he was wrong. They were good friends, and that was
all; and, as to the young lady’s heart, I had just as much reason as
Orsden—which was none whatever—for claiming a particular share
in its interest. Any thought of preference would have been rank
presumption in either of us, and the wish, I am sure, was founded
upon no such supposition. It was merely that with Hugh in his
present mood, the prospect of spending further hours in his company
was not an exhilarating one.
He was flushed, and lethargic, and very difficult to move to further
efforts when the meal was over; but we got him out at last and went
to work. It did not last long with him. It must have been somewhere
short of three o’clock that he shouldered his gun and came plodding
to me across the stubble.
“Look here, Viv,” he said, “I’m going home. Make my apologies to
Orsden, and keep it up with him; but I’m no good, and I’ve had
enough of it.”
He turned instantly with the word, giving a short laugh over the
meaning expressed obviously enough, I dare say, in my eyes, and
began to stride away.
“No,” he called, “I’m not going to shoot myself, and I’m not going to
let you make an ass of me. So long!”
I had to let him go. Any further obstruction from me, and I knew
that his temper would have gone to pieces. I gave his message to
Orsden, and we two continued the shoot without him. But it was a
joyless business, and we were not very long in making an end of it.
We parted in the road—Orsden for the Bit and Halter and the turning
to Leighway, and I for the gates of Wildshott. It was near five o’clock,
and a grey still evening. As I passed the stables, a white-faced
groom came hurrying to stop me with a piece of staggering news.
One of the maids, he said, had been found murdered, shot dead,
that afternoon in the Bishop’s Walk.

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Fundamentals of Analytical Chemistry

3rd Edition By Douglas A. Skoog

Fundamentals of Analytical Chemistry - Student Solution

Principios de análisis instrumental 7th Edition Douglas

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Carbon Dots in Analytical Chemistry: Detection and

Principles of Chemistry: A Molecular Approach 3rd

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indicator solvent chosen.

Reprinted by permission of the Hach Company

1 H IIA IIIA IVA VA VIA H He

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3 Na Mg IIIB IVB VB VIB VIIB IB IIB Al Si P S Cl Ar

7 Fr Ra Ac Rf Db Sg Bh Hs Mt Ds Rg Cn Uut Fl Uup Lv Uus Uuo

TO ACCOMPLISH THIS TASK TYPE THESE KEYSTROKES

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H2O 1 I32(aq) 1 H3AsO3(aq) S d 3I2(aq) 1 H3AsO4(aq) 1 H1(aq)

I32(aq) 1 2Fe(CN)64−(aq) S d 3I2(aq) 1 2Fe(CN)63− (aq)

Color Plate 4 The common-ion effect.

equilibrium shifts to the left to form more

Color Plate 7 When dimethylglyoxime

Color Plate 12 Reaction between Iron(III) and

iodide. The species in each beaker are indicated by

Color Plate 15 Series of standards (left) and two

(see Section 8C-2, page 172). The equation for the

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580 590 600 610 620 630 640

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Fe (Dr. Donald Mickey)

Fluorescent screen Shadow

Liquid Mercury vapor

Mercury vapor lamp White light source

Color Plate 19 Weighing by

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Part I Tools of Analytical Chemistry 14

Part II Chemical Equilibria 196

Part III Classical Methods of Analysis 279

Part IV Electrochemical Methods 441

Part V Spectrochemical Methods 649

Part VI Kinetics and Separations 818

Part VII Practical Aspects of Chemical Analysis 959

Chapter 35 The Analysis of Real Samples 960

Answers to Selected Questions and Problems A-34

Chapter 28 Atomic Spectroscopy 773 Chapter 34 Miscellaneous Separation Methods 935

Chapter 29 Mass Spectrometry 802 PART VII Practical Aspects

Glossary G-1 Appendix 7 Volumetric Calculations Using Normality and

T he ninth edition of Fundamentals of Analytical Chemistry is an introductory

Coverage and Organization

including supercritical fluid chromatography, capillary electrophoresis, and

To get access, visit ACKNOWLEDGMENTS

We especially acknowledge the assistance of Professor David Zellmer, California State

A nalytical chemistry is a measurement science consisting of a set of powerful ideas

1A The Role of Analytical Chemistry

in a chemical reaction can be calculated from quantitative measurements made

Unless otherwise noted, all content on this page is © Cengage Learning.