Che 029 Notescompleted

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CHE 029 Notes(Completed)
Analytical Chemistry (Qualitative and Quantitative Chemistry) (Southwestern University

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Prepared by: Kimberly D. Caballero, RMT Instructor: Julius Cezar Sario de Dios
SAS 1: REVIEW ON BASIC CHEMISTRY AND

INTRODUCTION TO ANALYTICAL CHEMISTRY
Qualitative Analysis
ANALYTICAL CHEMISTRY
 establishes the chemical identity of the
 Is a measurement science consisting of a set of species in the sample.
powerful ideas and methods that are useful in
all fields of science, engineering, and medicine Quantitative Analysis
 July 4, 1997
 the Pathfinder spacecraft delivered the  determines the relative amounts of these
Sojourner rover to the Martian surface species, or analytes, in numerical terms.
 January 2004
Analytes
 the Mars rovers Spirit and Opportunity
arrived on Mars for a three-month mission  are the components of a sample that are
 major result from Spirit’salpha particle X- determined
ray spectrometer (APXS) and Mossbauer
spectrometer was finding concentrated REVIEW OF BASIC CHEMISTRY
deposits of silica and, at a different site,
CHEMISTRY
high concentrations of carbonate
 Spirit  the science that deals with the study of the
 continued to explore and transmit data until changes in composition which matter
2010 undergoes and the transformation of energy
 Opportunity accompanying these changes
 had covered more than 21 miles exploring
and transmitting images of craters, small BASIC PRINCIPLES OF CHEMISTRY
hills, and other features by March 2012  Matter
 Curiosity
 is anything that occupies space and has
 was launched in late 2011 by Mars Science
mass (Solid, Liquid, Gas)
Laboratory
1. Physical (Intrinsic & Extrinsic)
 arrived on August 6, 2012 with a host of
 it is how the matter appears in nature
analytical instruments on board.
 Chemistry and Camera package includes:  ex. Color, odor, taste, texture, boiling,
freezing, melting, & etc.
 laser-induced breakdown spectrometer (LIBS)
2. Chemical
 provide determination of many
elements with no sample
 the property that enters into chemical
reactions
preparation
3. Physiological
 can determine the identity and
amounts of major, minor, and
 the psychological behavior when taken into
the body
trace elements and can detect
hydrated minerals  Changes of Matter
 remote micro imager 1. Physical - involves in the changes in form
 sample analysis package contains: and appearance, but without affecting their
o quadrupole mass spectrometer chemical nature.
2. Chemical - involves the change in its
o gas chromatograph
composition
o tunable laser spectrometer
 Classification of Matter
 survey carbon compound
1. Atom - the smallest particle of an element
sources, search for organic
which enters into a chemical combination,
compounds important to life,
composed of a nucleus and around it revolves
reveal the chemical and isotopic
the electrons.
states of several elements,
2. Molecule - is the smallest particle of matter
determine the composition of
that can exist in a free state capable of entering
the Martian atmosphere, and
into chemical change and is a combination of
search for noble gas and light
atoms of the same kind or different atoms.
element isotopes.
3. Element - simplest particle of matter which is
incapable of being divided and can enter into
chemical combination. It cannot be
decomposed into simpler materials by ordinary
processes.
Date: 12-01-22 Subject: CHE 029 (Analytical Chemistry) - Lecture

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4. Mixture- is a mass if ingredients with a variable 3. Metamorphous - the same

proportion; compound but they can be changed
a. Heterogeneous mixture is a into one form to another.
combination of 2 or more substances
Ex. Chalk—which can be changed to
which can be separated one from the
marble, having the same chemical
other by mechanical means (Filtration,
formula as calcium carbonate
floatation, centrifugation, distillation,
fractional distillation, fractional 4. Isomeric - a class of organic
compounds in which compounds
distillation, fractional crystallization, having the same molecular formula,
chromatography). but differs in physical and chemical
b. Homogenous mixture is a combination properties and the phenomenon is
of 2 or more substances which cannot termed as isomerism.
be separated from one another by
mechanical means, even by filtration Ex. ethyl alcohol and dimethyl ether
and decantation
5. Compound - a combination of two or more 5. Polymer - is a class of organic
elements at a definite proportion. It must compounds in which two or more
conform to a general law that a compound compounds have the same
would always have definite composition at a percentage of elements present in
definite proportion. the compound.
 If the molecules of the
Compound Characteristics: compound is taken twice, it is
1. They cannot be separated into their termed as Monomer
component substance by chemical  if more than twice it is termed
means. as Polymer and the
2. They are homogenous in phenomenon is termed
composition. polymorphism.
3. They have definite proportion by  According to its behavior as acid, base,
weight of the substance from which and salts:
they were made
ACIDS
 is a substance that produces hydrogen ion
when dissolved in water. (formula=HX; where X
is a monoatomic or polyatomic anion
 Other acid theories:
1. Bronsted-Lowry Theory
= an acid is a proton donor
2. Lewis Electronic Theory
= an acid is an electron acceptor
Classification of Compound Properties of acid
 According to the number of elements 1. Sour in taste
present 2. Neutralizes base
1. Binary, Ternary, Quaternary 3. Donor of proton
 According to form 4. pH below 7
1. Isomorphous - termed applicable if 5. feels like water on normal skin but it sting
the different compounds crystallize 6. turn red litmus paper to red
in the same form which is also
known as isomorphism.
Ex. Potassium permanganate &

potassium chlorate
2. Polymorphous - compounds
forming 2 or more different types of
crystals also known as
polymorphism.
Ex. Carbon

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Rules in naming acids:  atom has a small, dense nucleus that

contains protons and neutrons.
1. When the name of the anion (X) ends in –ide,
 Most of the mass of the atom is
the acid name begins with the prefix hydro.
concentrated in the nucleus.
The stem of the anion has the suffix –ic and it
 Collectively, the protons and neutrons are
is followed by the word acid. or All binary
called nucleons
acids have a prefix of –hydro and a suffix of –
ic Subatomic Particles:
ex. H2S --- hydrosulfuric acid 1. Electron–found in the region surrounding
the nucleus
HF --- hydrofluoric acid
2. Proton
2. When the anion ends in –ite, like sulfite, the 3. Neutron – no charge
acid name is the name of the anion with the  Mass number (A) = P + N
suffix –ous followed by the word acid.  Atomic number (Z) = P = E
ex. H3PO3 where
 John Dalton’s atomic theory:
X=phosphite = Phousphorous  Atom cannot be created or destroyed
acid)  Each elements is composed of extremely small
particles called atoms
3. If the anion name ends in –ate such as nitrate,
 All atoms of a given element are identical to one
the acid name is the anion with the suffix –ic,
another in mass other properties, but the atoms
followed by the word acid. HNO3 X=nitrate =
of one element are different from the atoms of
Nitric acid)
the other elements
BASE  The atoms of one element cannot be changed
into atoms of a different element by chemical
 substance that produces hydroxide ion when reactions; atoms are neither created nor
dissolved in water. destroyed in the chemical reactions
 Ionic compounds that are bases are named as
any other compounds: the name of the cation  Joseph John Thomson
is written first allowed by the name of the  proposed that atom is sphere of positive (+)
anion. Ex. KOH is potassium hydroxide particles to which are embedded with negative
particles.
 developed the Raisin-Bread Model or Plum-
Properties of Base Pudding Model.
1. Bitter in taste  Ernest Rutherford
2. Neutralizes acid  disproved Thomson’s model by using “Gold Foil-
3. Proton acceptor Film Experiment” in which he concluded that
4. pH above 7 atom is just an empty space, the nucleus
5. it feels smooth accounts for the positive charge & mass of the
6. soothing and slippery skin is atom then electrons are scattered around the
broke nucleus.
7. turn red litmus paper to blue  developed the Nuclear Model.
 Neils Bohr
SALTS  developed the ‘Planetary Model’ of atom
 defined as a substance whose water solution
 in which he proposed that atom consists of
contains a positive ion other than the hydrogen nucleus and surrounded by electrons which
ion and a negative ion other than the are travelling in circular orbits called
hydroxide ion. orbitals.
 Erwin Schrodinger
ATOM  developed the “Quantum Mechanical Model”
 this is considered the modern atomic
 the smallest particle of an element that retains structure.
its chemical identity.
 Democritus (460-370 BC) DIVISION OF CHEMISTRY
= a Greek philosopher who proposed
that all matter is composed of tiny  PURE (Inorganic, Organic, Physical, Analytical)
indivisible particles and called these  APPLIED (Industrial, Pharmaceutical Chemistry)
particles atomos which meant
indivisible or indestructible.

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THE ROLE OF ANALYTICAL CHEMISTRY A TYPICAL QUANTITATIVE ANALYSIS

 Deals with the accurate quantitative and 1. Choosing a Method
qualitative measurement of a chemical + The selected method usually represents a
substance to determine the exact possible compromise between the accuracy required
findings whether it may be an illnesses, drugs, and the time and money available for the
experiments & etc. analysis.
+ A second consideration related to economic
factors is the number of samples that will be
analyzed.
+ the complexity of the sample and the number
of components in the sample always influence
the choice of method to some degree.
2. Acquiring the Sample
 To produce meaningful information, an analysis
must be performed on a sample that has the
same composition as the bulk of material from
which it was taken.
 When the bulk is large and heterogeneous,
great effort is required to get a representative
sample
 A material is heterogeneous if its
constituent parts can be distinguished
visually or with the aid of a microscope
 Assay is the process of determining how
much of a given sample is the material by its
QUANTITATIVE ANALYTICAL METHODS indicated name. For example, a zinc alloy is
assayed for its zinc content, and its assay is
 2 Measurements a particular numerical value.
 the mass or the volume of sample being  Sampling - is the process of collecting a
analyzed small mass of a material whose composition
 some quantity that is proportional to accurately represents the bulk of the
the amount of analyte in the sample material being sampled
such as mass, volume, intensity of light,  Sample matrix/Matrix - is the collection of
or electrical charge all of the components in the sample
 Gravimetric Method containing an analyte
 we determine the mass of the analyte or some  We analyze samples, and we determine
compound chemically related to it substances. For example, a blood sample is
 Volumetric Method analyzed to determine the concentrations of
 we measure the volume of a solution containing various substances such as blood gases and
sufficient reagent to react completely with the glucose. We, therefore, speak of the
analyte. determination of blood gases or glucose, not
 Electroanalytical Method the analysis of blood gases or glucose.
 we measure electrical properties such as 3. Processing the Sample
potential, current, resistance, and quantity of  Preparing a Laboratory Sample
electrical charge  a solid laboratory sample is ground to
 Spectroscopic Method decrease particle size, mixed to ensure
 explore the interaction between homogeneity, and stored for various lengths
electromagnetic radiation and analyte atoms or of time before analysis begins
molecules or the emission of radiation by .
analytes.  Defining Replicate Samples
 Miscellaneous Method  most chemical analyses are performed on
 measure such quantities as mass-to-charge ratio replicate samples.
of ions by mass spectrometry, rate of o Replicate samples/replicates, are
radioactive decay, heat of reaction, rate of portions of a material of approximately
reaction, sample thermal conductivity, optical the same size that are carried through
activity, and refractive index. an analytical procedure at the same
time and in the same way
 replication improves the quality of the
results and provides a measure of their
reliability
 Quantitative measurements on replicates
are usually averaged, and various statistical

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tests are performed on the results to  computations are based on the raw
establish their reliability experimental data collected in the
measurement step, the characteristics of the
 Preparing Solutions: Physical & Chemical measurement instruments, and the
Changes stoichiometry of the analytical reaction
 most analyses are performed on solutions
of the sample made with a suitable solvent 7. Evaluating Results by estimating Realibility
o Ideally, the solvent should dissolve the  experimenter must provide some measure of
entire sample, including the analyte, the uncertainties associated with computed
rapidly and completely results if the data are to have any value
 converting the analyte in such materials into
a soluble form is often the most difficult and
time-consuming task in the analytical
process
o sample may require heating with
aqueous solutions of strong acids,
strong bases, oxidizing agents, reducing
agents, or some combination of such
reagents
4. Eliminating Interferences
 once we have the sample in solution and
converted the analyte to an appropriate form
for measurement, the next step is to eliminate
substances from the sample that may interfere
with measurement
 species other than the analyte that affect
the final measurement are called
interferences, or interferents
o is a species that causes an error in an
analysis by enhancing or attenuating
(making smaller) the quantity being AN INTEGRAL ROLE FOR CHEMICAL ANALYSIS:
measured. FEEDBACK CONTROL SYSTEM
 A scheme must be devised to isolate the  Analytical chemistry is usually not an end in
analytes from interferences before the final itself but is part of a bigger picture in which the
measurement is made. No hard and fast analytical results may be used to help control a
rules can be given for eliminating patient’s health, to control the amount of
interference. mercury in fish, to control the quality of a
 This problem can certainly be the most product, to determine the status of a synthesis,
demanding aspect of an analysis. or to find out whether there is life on Mars.
5. Calibrating and Measuring Concentration  Chemical analysis is the measurement element
 All analytical results depend on a final in all of these examples and in many other cases
measurement X of a physical or chemical
property of the analyte
 . This property must vary in a known and
reproducible way with the concentration cA
of the analyte
o Ideally, the measurement of the
property is directly proportional to the
concentration, that is, cA = kX
o where k is a proportionality constant.
o The process of determining k is thus an
important step in most analyses; this
step is called a
calibration
 (process of determining the proportionality
between analyte concentration and a measured
quantity.)  Feedback system is the process of
continuous measurement and control
 Feedback loop is the cycle of measurement,
comparison, and control.
6. Calculating results
SAS 2: ELECTROLYTES AND TRACE ELEMENTS
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ion to be determined and reveals

concentration of an analyte.
ELECTROLYTES  SPECTROSCOPIC METHODS
 it is based on the measurement of the
 Electrolytes and blood chemistries are usually
interaction between electromagnetic radiation
the first set of laboratory tests ordered upon
and analyte atoms or molecules or on the
initial patient presentation.
production of such radiation by analytes.
BASIC METABOLIC PANEL (BMP)  ION-SELECTIVE ELCTRODES (ISE)
 ionization of molecules introduced into a Mass
 includes sodium, Potassium, Chloride, Carbon Spectrometry (MS) involves ionization of
dioxide (CO2), glucose, Blood urea nitrogen molecule in the gas phase according to their
(BUN), and creatinine mass to charge ration (m/z).
 an abbreviated method for reporting the BMP  This assay is commonly used to test for
is: electrolytes.
 GAS CHROMATOGRAPHY (GC)
 it is use to identify and quantify volatile
substances such as alcohols.
 For toxicological screening of organic acids, and
drugs (e.g. steroids, benzodiazepines and
COMPREHENSIVE METABOLIC PANEL (CMP) tricyclic antidepressant).
 Has similar principle with thin layer
 includes albumin, Alkaline phosphatase, Alanine
chromatography but instead of solvent, GC
Aminotransferase (ALT), Aspartate
utilizes an inert gas (e.g. helium, nitrogen) as a
aminotransferase (AST), total bilirubin, and
carrier for the volatile substance.
Calcium, in addition to the components of the
 HIGH PERFORMANCE LIQUID
BMP.
CHROMATOGRAPHY (HPLC)
 Other examples of biochemical profile are SMA-
 it is widely used, especially in forensic
6, SMA-12 and Chem Profile 20.
laboratories, for toxicological screening , amino
COMMON ANALYTICAL METHODS & acids and drugs (e.g. indomethacin, anabolic
steroids, cyclosporine).
TECHNIQUES/ASSAY  It has similar principle with GC but it is useful in
 GRAVIMETRIC METHOD non-volatile or heat sensitive substance but
 determine the mass of the analyte or some instead of gas, HPLC utilizes a liquid solvent
compound chemically related to it. (mobile phase) and a column packed with a
 Precipitation – substance to be determined stationary phase (e.g. silica base).
is converted to an insoluble precipitate  ENZYME-LINKED IMMUNOSORBENT ASSAY
which is collected and weighed (ELISA)
 Volatilization – Analyte r its decomposing  it is a heterogeneous Enzyme Immunoassay
products are volatized a, collected and (EIA) which employs the same basic principles
weighed. as Radioimmunoassay (RIA) except that
 VOLUMETRIC/ TRITIMETRIC METHOD enzyme activity rather than radioactivity is
 measure the volume of the solution containing measured.
sufficient reagent to react completely with the  commonly used in serologic tests to determine
analyte (e.g. Acid-Base and Redox). antibodies directed against a wide range of
 ELECTROANALYTICAL METHOD antigens such as rheumatoid factor, hepatitis B
 involve the measurement of such electrical antigen, other bacterial and viral antigen (e.g.
properties as potential, current, resistance and cytomegalovirus, HIV…) in the serum
quantity of electrical charge.  ENZYME MULTIPLIED IMMUNOASSAY (EMIT)
 Voltammetry – measurement of current as  it is a homogeneous EIA in which the enzyme is
a function of the applied voltage and reveals used as a label for a specific analyte especially
the reduction potential of an analyte in testing general chemistries (e.g. albumin,
 Coulometry - measurement of current and BUN, creatinine, glucose, cholesterol, bilirubin,
time needed to complete an total protein), enzymes (e.g. acid and alkaline
electrochemical reaction and reveals phosphatase, amylase, creatinine kinase),
concentration of an analyte. coagulation factors (e.g. antithrombin III,
fibrinogen, degradation products, heparin,
plasminogen) and some drugs for therapeutic
drug monitoring (e.g. aminoglycosides,
vancomycin, digoxin, antiepileptics,
antiarrhythmics, theophylline) and for drug
level toxicology (e.g. acetaminophen,
 Potentiometry - measurement of potential salicylate, barbiturates, TCAs, amphetamines,
of an ion electrode in equilibrium with an cocaine, opiates).
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 FLUORESCENT POLARIZATION IMMUNOASSAY  “Dietary inorganic macro-mineral”

(FPIA)  Predominant cation in the extracellular fluid
 - the most common form of immunoassay, is  Common cation of choice to optimize the
used to measure concentrations of many pharmaceutical utility of organic medicaments
serum analytes such as BUN and creatinine.  The normal daily diet contains 8-15 g (130-
 commonly used for therapeutical drug 260mmol) of NaCl and the body only requires 1-2
monitoring of some drugs (e.g mmol/day and the excess is excreted by the
aminoglycosides, vancomycin, antiepileptics, kidneys, which are the ultimate regulators of the
antiarrhythmics, theophylline, methotrexate, amount of sodium in the body.
digoxin, cyclosporine), general chemistries and
Precautions:
enzyme (e.g., thyroxine, triiodothyronine,
cortisol, amylase, BUN, lactate dehydrogenase,  Sodium promotes water retention in the tissues
creatinine, glucose, cholesterol and iron). thus should be given in caution in patient with
 POLYMEREASE CHAIN REACTION (PCR) cardiac and renal condition in which edema is a
 is the most frequently used in Nucleic Acid problem
Amplification.  Excess levels of sodium/salt may indicates:
 also used principally for detecting  ▪ High Blood Pressure
microbiological organisms and genetic disease  ▪ Stroke
including chlamydia, cytomegalovirus, Epstein-  ▪ Heart Failure
Barr virus, human immunodeficiency virus,  ▪ Osteoporosis
mycobacterium, and herpes simplex virus.  ▪ Stomach Cancer
 ▪ Kidney Disease and kidney stones
 Sodium citrate (Na3C6H7O5) can incorporated
ELECTROLYTES in blood sample collection tube to avoid blood
corpuscle adhering to inner wall and maximum
 Body fluids are solutions of inorganic and reduction of blood sample haemocytolysis.
organic solutes which are important to maintain  Sodium Chloride (NaCl) in the most common
internal homeostasis within the body so the salt that is use as an electrolyte replenisher
cells and tissues will have constant environment
 are classified as either anions (negatively Other information:
charged) that moved toward an anode, or  Specimens assayed for sodium include serum,
cations (positively charged) ions that moved heparinized plasma, whole blood, sweat, urine,
toward the cathode. feces or gastrointestinal fluids.
 Physiological electrolytes include Na+ , K+,
Ca2+ , Mg2+, Cl- , HCO3- , HPO4- , H2PO42- ,
SO42- , and some organic anions (e.g. Lactate).
 intracellular fluids contain K+, Mg2+, and PO4
POTASSIUM (3.5 – 5.2 mEg/L)
-,2- ions;  It is derived from Kalium “the calcined ashes”;
 extracellular fluids (interstitial and plasma- which originally meant potash, an alkali
vascular fluids) holds the sodium, chloride, and extracted in a pot from the ash of burnt wood
bicarbonate ions. or tree leaves;
 In case an imbalance concentration occurs,  Easily oxidized (kept in kerosene, benzene, or
products like electrolytes, acids, base, blood liquid petrolatum)
products, carbohydrates, proteins, and amino  Makes glass amber-colored or light resistant
acids can be found.
 Electrolyte determination can be obtained from Pharmacological action/properties:
blood collected by venipuncture into an  Predominant intracellular cation necessary for
evacuated tube. cell growth and function
 Serum electrolyte concentrations are among  possesses an osmotic diuretic effect
the most commonly used laboratory tests by
clinicians for assessment of a patient’s clinical  Order of diuretic efficiency:
condition and disease state. nitrate > chloride > bicarbonate = acetate = citrate
SODIUM (Normal values: 135-147 mEg/L)  Potassium supplements should not be

administered by rapid IV injection
Properties:  Deficiency of K (hypokalemia/hypopotassemia)
 This ion belongs in Group IA (Alkali metal / may occur by:
Soluble group) in the periodic table together with  diarrhea
Li, K, Rb, Cs, Fr  hemorrhage
 Found abundantly and widely distributed in  diabetic coma
nature, but always in combination  vomiting
 A component of many minerals, and an essential Symptom/s: muscle weakness
element for animal life

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 Remedy: KCl (IV), Darrow’s solution (KCl + NaCl  Essential in the maintenance of normal body
with Na lactate) functions:
Excess K (hyperkalemia/hyperpotassemia): diastolic  Important cation for the normal functioning
arrest of the ANS
 Remedy: IV injection of NaCl, CaCl2, calcium  Important factor in cardiac function
gluconate, or dextrose  Factor in blood coagulation
Other information  Structural basis of the skeleton
 Specimens assayed for sodium analysis are  Absorbed in the upper portion of the intestinal
generally applicable to those for K+ analysis tract
 Possesses a cardiac action similar to digitals
MAGNESIUM (1.5 – 2.6 mg/L)  Excess Ca: systolic arrest (while excess K:
diastolic arrest)
 A group IIA (Alkali Earth metals: Be,Mg, Ca, Sr,  Absorption is enhanced with Vitamin D
Ba, Ra) ion which came from the origin,  Controls and relieves various allergic
magnesia manifestations (e.g. eczema, pruritus, urticaria)
 Widely and abundantly distributed in nature  Insoluble Ca salts are used as antacids (e.g.
 Second most abundant cation intracellularly CaCO3, tribasic Ca3(PO4)2)
 Element present in chlorophyll  Calcium chloride (Muriate of Lime) is a
 Occurs in bones (as Mg3(PO4)2) components of Ringer’s & Lactated Injection
 A component of “Flash-light” powders (a which are used as electrolyte --- can also
mixture of powdered Mg and K chlorate or decrease blood clotting time
barium peroxide)  Calcium citrate
 Used in pyrotechnics, tracer bullets, fire-
bombs, and night flares CHLORINE (95-106mEq/L)
Pharmacological Action and Uses:  From chloros meaning “greenish-yellow”
 CNS depressant in obstetrics, convulsant states,  Aka dephlogisticated marine acid or
and symptoms of tetanus dephlogisticated muriatic acid
 Exerts blocking action to acetylcholine at the  It is a Halogen ( F, Cl, Br, I, At) which also
neuromuscular junction (similar to curare: referred as salt forming group.
depresses sensitivity of the muscle to ACh)  It is the most abundant anion outside the cell.
 Antidote: Calcium  Hydrochloric acid (Gastric acid, Muriatic acid) is
 Natural calcium blocker the only acid found in the GIT.
 Saline laxative  Achlorhydria is a condition associated to the
absence of HCl in the GIT.
 Magnesium sulfate heptahydrate is one of the
most important compound of Magnesium that is: PHOSPHATES: Hydrogen Phosphate
 use as Saline cathartic,
(-HPO4-2), diHydrogen Phosphate (-H2PO4-)
 Antidote for barium and barbiturate
poisoning,
Hydrogen
 Anticonvulsant in eclampsia (IM),
 Recognized by Paracelsus
 Depressant in seasickness, HTN, tetanus
 Produced by Cavendish by the action of dilute
spasm, and convulsions (as IV or IM),
HCl and H2SO4 and called it inflammable air
 Used in paroxysmal auricular and ventricular
 Named by Lavoisier as hydrogen which means
tachycardia (IV)
water-former
 Properties:
 Lightest gas and the lightest of all elements
 Powerful reducing agent
CALCIUM (8.5 – 10.8 mg/dL)  Combustible but does not support
 Never found free in nature combustion
 Present inside the cell but most abundant  Element present in all acids
outside the cell.  Burns in air with a pale-blue, nonluminous
 Present in bones and teeth as apatite (Ca2(PO4)2) flame
 In non-luminous flame, imparts a brick red color
(reddish-yellow color) Phosphorous
 Occurs in combination as calcium phosphate
Pharmacological Action: (aka phosphorite or phosphate rock)
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 Occurs in bones and teeth (58% calcium  Rarely occurs in its elemental state in nature
phosphate), blood, urine, and in nervous,  Uses:
muscle, and brain tissue (as phosphoproteins)  Used in glass industry to make red-colored
 Lethal poison (large doses) glass
 Antidote for P poisoning: CuSO4 or blue vitriol  Essential trace element
 Antioxidant, synergistic with Vitamin E
Oxygen  Deficiency of Se will result to Keshan disease ;
 Also called:  If the deficiency is also associated with iodine, it
o Empyreal air (Scheele) – only known will result to Kashin-Beck disease.
supporter of combustion
o Fire air (Scheele) IODINE
o Dephlogisticated air (Priestley) - oxygen  From iodes meaning “violet”
does not burn, it only supports  Bluish-black rhombic plates that stains the skin
combustion brown
o Acid former (Lavoisier) – once thought  Normal constituent of the thyroid gland
as a constituent of all acids  Uses:
 Most abundant essential element in the  Essential for thyroid function
universe  Antiseptic
 Uses:  Expectorant (iodide ion)
o Pharmaceutical inhalant – used in  Iopanoic acid, USP – visualization of gall
pathological conditions (e.g. bladder
pneumonia, angina, asthma, bronchitis,  Preparation:
conditions accompanied by cyanosis  henolated iodine solution (Boulton’s
and dyspnea) solution) – antibacterial and irritant
o Component of “artificial air” (20%  Polyvinylpyrrolidone + Iodine (Povidone-
Oxygen and 80% Helium) – used to Iodine, Betadine®) – antiseptic
alleviate difficult respiration  Iodides (e.g. NaI, KI) – enhance the solubility of
o For oxidation reactions/combustion – iodine
required for burning  Antidote for iodine toxicity: cornstarch and
sodium thiosulfate
Phosphate
 is important and widely distributed in human FLUORIDE
body.  From Greek fluo meaning “flow”
 In blood, organic phosphate esters are located  Most electronegative element
primarily within cells and incorporated into  Most reactive among the halogens
nucleic acids, phospholipids, phosphoproteins  Strongest oxidizing agent
and high-energy compounds such as adenisone  Essential element present in teeth and bones in
thriphosphate (ATP) . minimal quantities
 Inorganic phosphate is a major components of  Used as anticariogenic agent
hydroxyapatite in bone. Compounds:
 Phosphates are located primarily in 1. Fluorides – anticaries agent
Endoplasmic Reticulum a. Sodium fluoride (NaF) – for dental
prophylaxis
Other information:  dental fluorosis/mottled enamel – excess fluoride
 Inorganic phosphate is the fraction measured in consumed
serum and plasma in clinical laboratories.
COPPPER
 Reddish-colored metal that belongs in COINAGE
TRACE ELEMENTS metal group.
 are inorganic micronutrients present at very low  3 rd most malleable metal
concentrations in body fluids and tissue.  excellent conductor of heat and electricity
 3 rd best conductor of electricity
SELENIUM  essential trace element
 From the Greek selene meaning “moon”  occurs in the respiratory pigment, hemocyanin
 It belongs in group VIA together with oxygen,
sulfur, tellurium and polonium

lOMoARcPSD|29701429
 Hemocyanin – bluish pigment found in the blood  Permanganates – powerful oxidizing agents
of some arthropods and mollusks that transports (0.02%-0.1% for urethral injections)
oxygen to tissues  Used in the manufacture of glass, colored
Pharmacological Action bricks, dryer in paints and varnishes
 essential to the metabolic process
 potential aid to iron assimilation MOLYBDENUM
 enhances physiological utilization of iron  Group VIB transition metal which is a silvery-
 emesis (due to irritant action) white, high-melting metal
 Wilson’s disease – a rare hereditary disease  Potentiates the uptake of iron in the body
resulting from the inability to metabolize copper  A cofactor of several mammalian enzymes
leading to the deposition of toxic amounts of (sulfite oxidase, xanthine dehydrogenase and
copper in various tissues (e.g. eye, liver, brain, aldehyde oxidase)
kidney)
o Treatment: Penicillamine (Cuprimine)
IRON
 promotes urinary excretion of
 It is an important constituent of the blood
excess copper
(hemoglobin) and oxidases (cytochrome
Uses:
oxidase)
 Protein precipitant (astringent to mucous
 absorption is enhanced with Vitamin C
membranes)
 Hematite – most important source of iron
 Effective fungicide in minute amounts
 Algaecide
Pharmacological Action & Uses:
 Bacteriostatic antiseptic
 Externally: Protein precipitant and astringent
(ferric salts)
ZINC  Internally: Formation of hemoglobin
 Present in ores  Mucosal block – best known of the three
o sphalerite or zinc blende (ZnS) hypotheses on iron absorption
o smithsonite (ZnCO3)  Ferritin – iron-carrying protein; stores iron
 bluish-white metal  Transferrin or siderophilin – transports iron
 when a zinc salt is heated with any cobalt salt →  Hemochromatosis – too much iron builds up in
cobalt zincate (Rinmann’s green) the body
Pharmacological Action: Iron Preparations:

 Present in highest concentrations in testes, hair  Ferrous salts are indicated for the treatment of
and nails, bone, and pigmented tissues of the “secondary anemias”.
eye  Secondary anemias are also classified as
 Present in carbonic anhydrase (enzyme in blood “hypochromic microcytic anemias” indicating a
cells that aids in the transfer of carbon dioxide low hemoglobin content and small size cells.
from the tissues to the lungs)
 Possesses emetic action and strong local 1. Ferrous sulfate
astringent action when ingested  aka Green Vitriol, Copperas
 Antidote for zinc poisoning: NaHCO3  stable form of iron
 most economical and most satisfactory form
CHROMIUM of iron in the market
 Group VIB transition metal  hematinic (increases blood hemoglobin)
 A glucose tolerance factor – used for improving  oxidizes readily on exposure to moist air
blood sugar control in diabetic people; acts as a forming crystals coated with brownish-yellow
physiological enhancer of insulin activity, basic ferric sulphate
binding to insulin and potentiating its action
COBALT
MANGANESE  Pure cobalt – pinkish-white metal
 Essential trace element (traces occur in almost  Cobaltous salts – pink (hydrated); blue
all organs of both man and animals) (anhydrous)
 Cofactor involved in protein synthesis,  Essential in the development of erythrocytes
phosphorylation, and fatty acid & cholesterol and hemoglobin (small quantities)
synthesis  Stimulates the bone marrow
 Possible synergistic action with iron  Present in Vitamin B12 (Cyanocobalamin)

lOMoARcPSD|29701429
 Used in the manufacture of beer (stabilize after a hard workout or a bout of stomach flu —
foaming quality) you’ve suddenly lost a lot of electrolytes
 In the 1960s, some breweries added cobalt through fluids. Other times to watch out for
salts to beer to stabilize the foam (resulting electrolyte imbalances include prolonged
in exposures of 0.04–0.14 mg cobalt/kg). dehydration, high fevers, kidney problems,
 Cobalt (II) chloride or cobaltous chloride physical trauma such as burns, and switching
(CoCl2) – aka Sympathetic ink or Lover’s medications or starting a new one. Health
ink; indicator in silica gel beads conditions such as kidney or heart disease or
diabetes can also increase your chances of
FAQS developing an electrolyte imbalance, as well as
1. How does an electrolyte imbalance affect my eating disorders such as bulimia or anorexia
body? nervosa.
 Your kidneys work together with several
hormones to keep each of your electrolytes
balanced at the correct levels. Since they
control so many bodily processes, having an
electrolyte imbalance can wreak havoc on your
health, and even develop into a lifethreatening
condition. Electrolyte imbalances can be
temporary and mild or prolonged and severe,
and usually involve one of the “big three”
electrolytes: potassium, sodium, and calcium.
Symptoms of a temporary disturbance include
dizziness, exhaustion, and muscle problems
such as cramps, twitching, numbness, and
fatigue. Some people may also suffer from
stomach cramps and nausea, dark urine, dry
mouth, and swelling from fluid retention. Signs
of a more several imbalance are irregular
heartbeat, changes in blood pressure, mental
confusion, and seizures or convulsions. If you
experience any of these symptoms, you should
seek medical help immediately.
2. When should I be looking out for electrolyte SAS 3: TOXIC METALS

imbalances?
 Since electrolytes are contained in bodily fluids,
any time you get rid of said fluids, you’re METAL TOXICITY/METAL POISONING
probably getting rid of some electrolytes too.
 is the toxic effect of certain metals in
Sweating, vomiting, diarrhea, and even
certain forms and doses on life
urination are all different ways you can lose
electrolytes. That’s why you feel so depleted
 Chelation Therapy
lOMoARcPSD|29701429
 a technique which involves the

administration of chelation agents to
remove metals from the body.
 Toxic Metals
 Thallium
 Cadmium
 Manganese
 Lead
 Mercury  Metals are measured in biological fluids
 Radioactive metals (have both using the following:
radiological toxicity & chemical toxicity)
 Metalloids (Arsenic, Polonium) may be  ATOMIC ABSORPTION SPECTROMETRY
included
 Elements in groups IB, IIB, IIIA, even IV
WITH FLAME (AAS-F) /
in row 6 & 7 (heavy metals) ELECTROTHERMAL ATOMIZATION
 Metals in an oxidation state abnormal to the FURNACE (AAS-ETA)
body may also become toxic:
 chromium(III) is an essential trace  INDUCTIVELY COUPLED PLASMA-
element, but chromium(VI) is a
OPTICAL EMISSION SPECTROMETRY
carcinogen
(ICP-OES)
 Bioaccumulation
 An increase in the concentration of a
chemical in a biological organism over  INDUCTIVELY COUPLED PLASMA-MASS
time, compared to the chemical’s SPECTROMETRY (ICP-MS)
concentration in the environment.
o Heavy metals are dangerous because  HIGH PERFORMANCE LIQUID
they tend to bioaccumulate.
CHROMATOGRAPHY-MASS
 Compounds accumulate in living things any
time they are taken up and stored faster
SPECTROMETRY (LC-MS)
than they are broken down (metabolized) or
excreted.
 PHOTOMETRIC ASSAY
 Heavy metals can enter a water supply by
industrial and consumer waste, or even  Are also possible but require large
from acidic rain breaking down soils and volumes of sample and have
releasing heavy metals into streams, lakes, limited analytical performance.
rivers, and groundwater.
 Heavy metal toxicity can result in:
BERYLLIUM
 damaged or reduced mental and
 It is an alkaline earth metal together with Mg, Ca,
central nervous function
Sr, Ba and Ra
 lower energy levels
 Once called glucinum because of the sweet taste
 damage to blood composition,
of its salts
lungs, kidneys, liver, and other vital
 Differentiated from magnesium by adding
organs.
quinalizarin + bromine water o Be: persistence of
 Long-term exposure may result in
blue color o Mg: disappearance of blue color
slowly progressing physical,
 Regarded as the most toxic metal
muscular, and neurological
o Inhibits carbohydrate metabolic cycle by
degenerative processes that mimic
Alzheimer's disease, Parkinson's preventing breakdown of phosphorus
disease, muscular dystrophy, and compounds
multiple sclerosis o Disturbs respiration, circulation, and
 Allergies are not uncommon and temperature
repeated long-term contact with o No specific antidote is known
some metals or their compounds  Never used in medicine
may even cause cancer.
 Used in the fluorescent lighting industry. Metallic,
Alloys and ceramics of Be are widely used in
dental appliances, wheelchairs, nuclear power
and neutron modulator.
 Chronic Berylium disease (CBD) is a chronic
respiratory condition due to chronic beryllium
exposure that is characterized by the formation of
granulomas resulting from immune reaction to Be
in the lungs.
lOMoARcPSD|29701429
 Symptoms do not occur immediately but are

typically delayed 12 to 14 hours after ingestion.
ALUMINUM  Acute effects include abdominal pain, nausea,
vomiting, and diarrhea (sometimes with
 It is most abundant metal and the 3rd most
hemorrhage). Shock may result from massive
abundant element
fluid or blood loss. Within 2-3 days, delirium,
Pharmacological Action & Uses:
seizures, respiratory failure, and death may
o may constrict the blood vessels
occur.
when applied topically
o astringent (inherent)
 Chronic effects include painful peripheral
neuropathy, myopathy, chorea, stomatitis, and
o antiseptic
ophthalmoplegia. Hair loss and nail dystrophy
o antiperspirant
(Mees' lines) may appear after 2-4 weeks.
o Aluminum powder – used as
o It is rapidly absorbed via ingestion, inhalation
inhalation in the treatment of
and skin contact. Sign and symptoms of
silicosis;
poisoning includes loss of hair, peripheral
o Used in burn treatment (aluminum
neuropathy, seizures, renal failure and may also
foil): protects the burn and
cause green tongue.
conserves fluid and stimulates
o Diagnosis. Thallotoxicosis should be considered
tissue growth;
when gastroenteritis and painful paresthesia are
o Toxicity to aluminum has been
followed by alopecia.
linked with oral exposure to  Specific levels. Urinary thallium is normally less
aluminum containing
Note: Evacuated than 0.8 mcg/L. Concentrations higher than 20
pharmaceutical products like
mcg/L provide evidence of excessive exposure
blood collection antacids;
and may be associated with subclinical toxicity
devices used in = Patients with renal failure has
during workplace exposures. Blood thallium
phlebotomy have high risk of aluminum toxicity.
levels are not considered reliable measures of
rubber stoppers = Aluminum accumulate in
exposure except after large exposures. Hair
that are made of blood and binds tightly in protein
levels are of limited value, used mainly in
aluminum silicate (e.g. transferrin) and is rapidly
documenting past exposure and in forensic
distributed throughout the body.
that when cases.
= Aluminum overload may
punctured during  Other useful laboratory studies include CBC,
replace calcium in bone disrupting
blood collection electrolytes, glucose, BUN, creatinine, and
normal osteoid formation and may
may contaminate hepatic transaminases. Since thallium is
be reflected diagnostically with low
the sample with radiopaque, plain abdominal x-rays may be
parathyroid hormone (PTH).
useful after acute ingestion.
aluminum.
TREATMENT
 Emergency and supportive measures
1. Maintain an open airway and assist
ventilation if necessary (see Airway).
THALLIUM 2. Treat seizures (see Seizures) and coma
 is a soft metal that quickly oxidizes upon (Coma and stupor) if they occur.
exposure to air 3. Treat gastroenteritis with aggressive
 It is a minor constituent in a variety of ores. intravenous replacement of fluids (and
 Thallium salts are used in the manufacture of blood if needed). Use pressors only if
jewelry, semiconductors, and optical devices. shock does not respond to fluid therapy
 no longer is used in the United States as a (see Hypotension).
depilatory or a rodenticide because of its high
human toxicity.
o From thallos meaning “green twig”
o This can also be a by-product of lead  Specific drugs and antidotes. There is currently
smelting which can be very toxic no recommended specific treatment in the
United States. ▪
1. Prussian blue (ferric ferrocyanide) is
Mechanism of toxicity the mainstay of therapy in Europe and
 The mechanism of thallium toxicity is not known. received FDA approval for use in the
It appears to affect a variety of enzyme systems, United States in 2003.
resulting in generalized cellular poisoning. - This compound has a crystal lattice
Thallium metabolism has some similarities to that structure that binds thallium ions and
of potassium, and it may inhibit potassium flux interrupts enterohepatic recycling.
across biologic membranes by binding to Na-K ATP - Insoluble Prussian blue (Radiogardase)
transport enzymes. is available as 500-mg tablets, and the
o Primarily use as rodenticide recommended adult dose is 3 g orally
Clinical presentation

lOMoARcPSD|29701429
three times per day.Prussian blue particles of silicon and transport

appears to be nontoxic at these doses. them to lymph nodes where
- In the United States, Prussian blue they can accumulate.
should be available through  Silicosis – a lung condition
pharmaceutical suppliers. resembling chronic tuberculosis,
2. Activated charcoal is readily available developing after exposure to
and has been shown to bind thallium in respirable silica dust.
vitro.
- Multiple-dose charcoal is LEAD
recommended because thallium  is a soft, malleable metal that is obtained chiefly
apparently undergoes enterohepatic by the primary smelting and refining of natural
recirculation. ores or by the widespread practice of recycling
- In one study, charcoal was shown to be and secondary smelting of scrap lead products.
superior to Prussian blue in eliminating  Recycling accounts for nearly 85% of domestic
thallium. lead consumption, approximately 85% of which
3. BAL (see BAL [Dimercaprol]) and other is used in the manufacture of lead acid
chelators have been tried with varying batteries.
success.  Lead is used for weights and radiation
- Penicillamine and shielding, and lead alloys are used in the
diethyldithiocarbamate should be manufacture of pipes; cable sheathing; brass,
avoided because of studies suggesting bronze, and steel; ammunition; and solder
that they contribute to redistribution of (predominantly electrical devices and
thallium to the brain automotive radiators).
 Decontamination. Administer activated  Lead compounds are added as pigments,
charcoal orally if conditions are appropriate (see stabilizers, or binders in paints, ceramics, glass,
Table Iâ€“38). Ipecacinduced vomiting may be and plastic.
useful for initial treatment at the scene (eg,  Although the use of lead in house paint has
children at home) if it can be given within a few been curtailed since the 1970s, industrial use of
minutes of exposure. Consider gastric lavage for corrosion- resistant lead-based paint continues,
large recent ingestions. and high-level exposure may result from
 Enhanced elimination. Repeat-dose activated renovation, sandblasting, torching, or
charcoal may enhance fecal elimination by demolition.
binding thallium secreted into the gut lumen or  Young children are particularly at risk from
via the biliary system, interrupting repeated ingestion of lead contaminated house
enterohepatic orenteroenteric recirculation. dust, yard soil, or paint chips or from mouthing
Forced diuresis, dialysis, and hemoperfusion are toy jewelry or other decorative items containing
of no proven benefit. lead.
 Children may also be exposed to lead carried
SILICON into the home on contaminated work clothes
 It is 2nd most abundant element next to oxygen worn by adults.
but the most abundant elements in the  Lead exposure may occur from the use of lead-
environment glazed ceramics or containers for food or
 Compounds of Silicon beverage preparation or storage.
1. Colloidal silicon dioxide  Certain folk medicines (eg, the Mexican
o Used as adsorbent, desiccant, remedies azarcon and greta, the Dominican
thickener remedy litargirio, and some Indian Ayurvedic
preparations) may contain high amounts of lead
salts.
 It is a metal commonly found in the
2. Amorphous oxide of silicon environment (eg. Ceramics at home, paint,
(e.g.Asbestos) leaded gasoline, water pipes soldered with lead,
o Inhalation of asbestos- soil)
containing dust leads  Absorption is slow but action is cumulative;
asbestosis, deposition of accumulates and stored in bones.it can be
asbestos fiber in the pulmonary ingested, inhaled or through dermal contact.
alveoli.  Toxicity will result to impaired growth and
3. Methylated polymers of silicon mental development, decrease vitamin D and
o silicon implants have come to hemoglobin synthesis, nephropathy,
public attention. Encephalopathy and death.
o Silicon appears to induce a o Antidote
response from  Chelation of BAL
polymorphonuclear cells and  Dimercaprol
macrophages that bind small Mechanism of Toxicity
lOMoARcPSD|29701429
a. The multisystem toxicity of lead is mediated by 1. Acute symptomatic intoxication is rare

several mechanisms, including inactivation or after a single exposure but may occur
alteration of enzymes and other within hours after ingestion of gram
macromolecules by binding to sulfhydryl, quantities of soluble lead compounds or
phosphate, or carboxyl ligands and interaction days after GI retention of swallowed
with essential cations, most notably calcium, lead objects, such as fishing weights and
curtain weights.
zinc, and iron
2. Studies have not established a low-dose
may occur:
threshold for adverse subclinical effects
1. Pathologic alterations in cellular and of lead. Recent epidemiologic studies in
mitochondrial membranes children have observed effects of lead
2. neurotransmitter synthesis and on cognitive function at blood lead
function concentrations less than 5 mcg/dL, and
3. heme synthesis other studies suggest that background
4. cellular redox status levels of lead exposure in recent
5. nucleotide metabolism decades may have been associated with
b. Pharmacokinetics. hypertension in some adults. The
 Inhalation of lead fume or other fine, geometric mean blood lead
soluble particulate results in rapid and concentration in the United States
extensive pulmonary absorption, the during 2001â€“2002 was estimated to
major though not exclusive route of be 1.45 mcg/dL; background dietary
exposure in industry. lead intake may be in the range of
 Nonindustrial exposure occurs 1â€“4 mcg per day.
predominantly by ingestion, particularly in 3. The US Environmental Protection
children, who absorb 45-50% of soluble Agency action level for lead in drinking
lead compared with approximately 10- water is 15 ppb (parts per billion).
15% in adults. However, the Maximum Contaminant
 After absorption, lead is distributed via Level (MCL) goal for drinking water is
the blood (where 99% is bound to the zero ppb, and EPA has set no "reference
erythrocyte) to multiple tissues, including dose" for lead because of the lack of a
transplacental transport to the fetus, and recognized low-dose threshold for
CNS transport across the bloodbrain adverse effects.
barrier. o Inhalation. Unprotected exposure to the
 Clearance of lead from the body follows a
massive airborne lead levels (> 2500 mcg/m3)
multicompartment kinetic model,
encountered during abrasive blasting, welding,
consisting of "fast" compartments in the
or torch cutting metal surfaces coated with
blood and soft tissues (half-life of 1 to 2
lead- based paint poses an acute hazard and has
months) and slow compartments in the
resulted in symptomatic lead intoxication from
bone (half-life of years to decades).
within a day to a few weeks. The OSHA
 Approximately 70% of lead excretion
workplace permissible exposure limit (PEL) for
occurs via the urine, with smaller
inorganic lead dustsand fumes is 50 mcg/m3 as
amounts eliminated via the feces and
an 8-hour time-weighted average. The level
scant amounts via the hair, nails, and
considered immediately dangerous to life or
sweat.
health (IDLH) is 100 mg/m3.
 Greater than 90% of the lead burden in
adults and more than two-thirds of the
burden in young children occur in the
skeleton.
 Slow redistribution of lead from bone to
soft tissues may elevate blood lead
Clinical presentation.
concentrations for months to years after a
 The multisystem toxicity of lead presents a
patient with chronic high-dose exposure
spectrum of clinical findings ranging from overt,
has been removed from external sources.
lifethreatening intoxication to subtle, subclinical
 In patients with high bone lead burden,
effects.
pathologic states associated with rapid
o Acute ingestion of very large amounts
bone turnover or demineralization, such
of lead (gram quantities) may cause
as hyperthyroidism and immobilization
abdominal pain, anemia (usually
osteoporosis, have resulted in
hemolytic), toxic hepatitis, and
symptomatic lead intoxication.
encephalopathy.
Toxic dose
o Subacute or chronic exposure is more
 Dermal absorption is minimal with inorganic lead
common than acute poisoning.
but may be substantial with organic lead
 Constitutional effects include fatigue,
compounds, which may also cause skin irritation. malaise, irritability, anorexia, insomnia,
 Ingestion. In general, absorption of lead weight loss, decreased libido,
compounds is directly proportional to solubility arthralgias, and myalgias. Hypertension
and inversely proportional to particle size. may be associated with lead exposure in
Gastrointestinal lead absorption is increased by susceptible populations.
iron deficiency and low dietary calcium and  Gastrointestinal effects include crampy
decreased by co-ingestion with food. abdominal pain (lead colic), nausea,
lOMoARcPSD|29701429
constipation, or (less commonly) specific environmental exposure. Levels

diarrhea. between 5 (or lower) and 25 mcg/dL
 Central nervous system manifestations have been associated with subclinical
range from impaired concentration, decreases in intelligence and impaired
headache, diminished visualmotor
neurobehavioral development in
coordination, and tremor to overt
encephalopathy (a life-threatening children exposed in utero or in early
emergency characterized by agitated childhood. Studies in adults suggest that
delirium or lethargy, ataxia, convulsions, long-term blood lead concentrations in
and coma). Chronic low-level exposure in the range of 10-25 mcg/dL may pose a
infants and children may lead to risk for hypertension and might possibly
decreased intelligence and impaired contribute to age-related decline in
neurobehavioral development, stunted cognitive function.
growth, and diminished auditory acuity. o Blood lead levels of 25-60 mcg/dL may
Recent studies in adults suggest that
be associated with headache, irritability,
lead may accentuate age-related decline
difficulty concentrating, slowed reaction
in cognitive function.
 Peripheral motor neuropathy, affecting time, and other neuropsychiatric effects.
mainly the upper extremities, can cause Anemia may occur, and subclinical
severe extensor muscle weakness ("wrist slowing of motor nerve conduction may
drop"). be detectable.
 Hematologic effects include o Blood levels of 60â€“80 mcg/dL may be
normochromic or microcytic anemia, associated with GI symptoms and
which may be accompanied by subclinical renal effects.
basophilic stippling. Hemolysis may o With blood levels in excess of 80 mcg/dL,
occur after acute or subacute high-dose
serious overt intoxication may occur,
exposure.
 Nephrotoxic effects include reversible including abdominal pain (lead colic) and
acute tubular dysfunction (including nephropathy. Encephalopathy and
Fanconi-like aminoaciduria in children) neuropathy usually are associated with
and chronic interstitial fibrosis. levels over 100 mcg/dL.
Hyperuricemia and gout may occur.
 Adverse reproductive outcomes may Treatment
include diminished or aberrant sperm  Emergency and supportive measures
production, increased rate of o Treat seizures (see Seizures) and coma
miscarriage, preterm delivery, decreased (Coma and stupor) if they occur.
gestational age, low birth weight, and
o Provide adequate fluids to maintain
impaired neurologic development.
urine flow (optimally 1â€“2 mL/kg/h)
o Repeated, intentional inhalation of
but avoid overhydration, which may
leaded gasoline has resulted in ataxia,
aggravate cerebral edema.
myoclonic jerking, hyperreflexia,
o Avoid phenothiazines for delirium, as
delirium, and convulsions.
they may lower the seizure threshold.
Diagnosis  Patients with increased intracranial pressure
 abdominal pain may benefit from corticosteroids (eg,
 headache dexamethasone, 10 mg IV) and mannitol
 anemia (0.25â€“1.0 g/kg IV as a 20â€“25% solution).
 motor neuropathy  Specific drugs and antidotes
 gout o Encephalopathy
 renal insufficiency  Administer intravenous calcium EDTA
 Consider lead encephalopathy in any child or  Some clinicians initiate treatment
adult with delirium or convulsions (especially with a single dose of BAL (BAL),
with coexistent anemia) and chronic lead followed 4 hours later by concomitant
poisoning in any child with neurobehavioral administration of calcium EDTA and
deficits or developmental delays BAL.
o Symptomatic without encephalopathy.
 Specific level  . Administer oral succimer (DMSA,
 The whole-blood lead level is the most Succimer [DMSA]) or parenteral
useful indicator of lead exposure calcium EDTA
 Relationships between blood lead levels  . Calcium EDTA is preferred as initial
and clinical findings generally have been treatment if the patient has severe GI
based on subacute or chronic exposure toxicity (eg, lead colic) or if the blood
and not on transiently high values that lead concentration is extremely
may result immediately after acute elevated (eg, > 150 mcg/dL).
exposure  Unithiol (Unithiol [DMPS]) may be
 Note: Blood lead samples must be drawn and considered as an alternative to DMSA.
stored in lead-free syringes and tubes ("trace o Asymptomatic children with elevated
metals" tube or royal blue stopper tube containing blood lead levels
heparin or EDTA).  The Centers for Disease Control and
Prevention (CDC) recommend
o Blood lead levels are less than 5 mcg/dL treatment of children with levels of 45
in populations without occupational or mcg/dL or higher.
lOMoARcPSD|29701429
o Asymptomatic adults  Phenylarsenic compounds are used as feed

 The usual treatment is removal from additives for poultry and swine, and intravenous
exposure and observation arsenic trioxide, reintroduced to the US
 Consider oral succimer (DMSA, pharmacopoeia in 2000, is used as a drug for
Succimer [DMSA]) for patients with cancer chemotherapy.
markedly elevated levels (eg,> 80-100  Inorganic arsenic is used in the production of
mcg/dL).
nonferrous alloys, semiconductors, and certain
 Although D-penicillamine (see
types of glass.
Penicillamine) is an alternative oral
 Inorganic arsenic is sometimes found in folk
treatment, it may be associated with
more side effects and less efficient remedies and tonics, particularly from Asian
lead diuresis. sources.
o Blood lead monitoring during chelation  Artesian well water can be contaminated by
 Obtain a blood lead measurement inorganic arsenic from natural geologic deposits,
immediately prior to chelation and and elevated levels of arsenic may be
recheck the measurement within 24- encountered in mine tailings and sediments and
48 hours after starting chelation to coal fly ash.
confirm that levels are declining  Arsine, a hydride gas of arsenic, is discussed in
Arsine.
o Steel-gray brittle solid with a distinct
metallic luster
SILVER o It is widely known to be toxin that
gained notoriety from its extensive use
 Also called noble metal because of its use in by Renaissance and was known as
making articles of value (e.g. coins, ornaments, Poison of Kings and King of Poisons;
jewelry) o It is listed as number one toxicant in US.
 May be precipitated by HCl o It is also a known carcinogenic agent
Pharmacological Action and Uses:
Mechanism of Toxicity
 Protein precipitant  Arsenic compounds may be organic or inorganic and
 Antiseptic, astringent, and corrosive to tissues may contain arsenic in either a pentavalent
 Possesses oligodynamic action (arsenate) or a trivalent (arsenite) form.
 Treatment of burn (silver sulfadiazine) A. Soluble arsenic compounds, which are well
absorbed after ingestion or inhalation, pose the
Toxicity greatest risk for acute human intoxication.
 Discolors skin (argyria) which may result to B. Inorganic arsenic dusts (such as arsenic trioxide)
growth retardation, hemopoiesis, cardiac may exert irritant effects on the skin and mucous
enlargement, degeneration of the liver, membranes. Contact dermatitis has also been
destruction of renal tubules. reported. Although the skin is a minor route of
absorption for most arsenic compounds,
Antidote systemic toxicity has resulted from industrial
 6% Na2S2O3 + 1% K4Fe(CN)6 subcutaneously accidents involving percutaneous exposure to
but requires several injections into the affected highly concentrated liquid formulations.
area
C. The chemical warfare agent lewisite (dichloro [2-

chlorovinyl] arsine) is a volatile vesicant liquid
ARSENIC that causes immediate severe irritation and
 compounds are found in a select group of necrosis to the eyes, skin, and airways.
industrial, commercial, and pharmaceutical D. Arsenate and arsenite are known human
products. carcinogens by both ingestion and inhalation.
 Use of arsenic as a wood preservative in
industrial applications (such as marine timbers Toxic dose
and utility poles) accounts for two-thirds of
 The toxicity of arsenic compounds varies
domestic consumption, but former widespread
considerably with the valence state, chemical
use in new lumber sold for residential purposes
composition, and solubility.
(eg, decks, fencing, play structures) ended with
 Humans are generally more sensitive than other
a voluntary ban effective at the end of 2003.
animals to the acute and chronic effects of
 Arsenic-treated lumber used in residential
arsenicals.
structures and objects created prior to 2004 has
A. Inorganic arsenic compounds
not been officially recalled or removed.
1. Acute ingestion of as little as
 Arsenic-impregnated gels are used as ant baits,
100â€“300 mg of a soluble trivalent
and a few organoarsenicals, such as methane
arsenic compound (eg,sodium
arsonates and cacodylic acid, continue to be
arsenite) could be fatal.
used as herbicides and defoliants.
lOMoARcPSD|29701429
2. The lowest observed acute effect level  Although prominent gastrointestinal (GI)
(LOAEL) for acute human toxicity is symptoms may subside within 24 to 48
approximately 0.05mg/kg, a dose hours, severe multisystemic effects may
associated with gastrointestinal still ensue.
distress in some individuals. 2. Cardiovascular effects.
3. Death attributable to malignant  In severe cases, extensive tissue third
arrhythmias has been reported after spacing of fluids combined with fluid loss
days to weeks of cancer from gastroenteritis may lead to
chemotherapy regimens in which 0.15 hypotension, tachycardia, shock, and
mg/kg/day of arsenic trioxide was death.
administered intravenously.  Metabolic acidosis and rhabdomyolysis
4. Repeated ingestion of approximately may be present.
0.04 mg/kg/day can result in  After a delay of 16 days, there may be a
gastrointestinal distress and second phase of congestive
hematologic effects after weeks to cardiomyopathy, cardiogenic or
months and peripheral neuropathy noncardiogenic pulmonary edema, and
after 6 months to several years. Lower isolated or recurrent cardiac arrhythmias.
chronic exposures, approximately  Prolongation of the QT interval may be
0.01 mg/kg/day, can result in associated with torsade de pointes
characteristic skin changes (initially ventricular arrhythmia.
spotted pigmentation, followed within 3. Neurologic effects.
years by palmar-plantar  Mental status may be normal, or there
hyperkeratosis) after intervals of may be lethargy, agitation, or delirium.
5â€“15 years.  Delirium or obtundation may be delayed
5. The US National Research Council by 26 days.
(2001) estimated that chronic  Generalized seizures may occur but are
ingestion of drinking water containing rare.
arsenic at a concentration of 10 mcg/L  Symmetric, sensorimotor axonal
could be associated with an excess peripheral neuropathy may evolve 15
lifetime cancer risk greater than 1 in weeks after acute ingestion, beginning
1000. The latency period for with painful distal dysesthesias,
development of arsenic-induced particularly in the feet.
cancer is probably a decade or longer  Ascending weakness and paralysis may
B. Organic arsenic. ensue, leading in severe cases to
 In general, pentavalent organoarsenic quadriplegia and neuromuscular
compounds are less toxic than either respiratory failure.
trivalent organoarsenic compounds or 4. Hematologic effects.
inorganic arsenic compounds.  Pancytopenia, particularly leukopenia and
 Marine organisms may contain large anemia, characteristically develops within
quantities of arsenobetaine, an organic 12 weeks after acute ingestion.
trimethylated compound that is excreted  A relative eosinophilia may be present,
unchanged in the urine and produces no and there may be basophilic stippling of
known toxic effects. red blood cells
 Arsenosugars (dimethylarsinoyl riboside 5. Dermatologic effects.
derivatives) are present in some marine  Findings that occasionally appear after a
and freshwater animals (eg, bivalve delay of 1-6 weeks include desquamation
mollusks) and marine algae (eg,seaweeds (particularly involving palms and soles), a
often used in Asian foods). diffuse maculopapular rash, periorbital
edema, and herpes zoster or herpes
Clinical presentation
simplex.
A. Acute exposure most commonly occurs after  Transverse white striae in the nails
accidental, suicidal, or deliberate poisoning by (Aldrich-Mees lines) may become
ingestion. A single, massive dose produces a apparent months after an acute
constellation of multisystemic signs and intoxication.
symptoms that emerge over the course of hours B. Chronic intoxication is also associated with
to weeks. multisystemic effects, which may include fatigue
1. Gastrointestinal effects. and malaise, gastroenteritis, leukopenia and
 After a delay of minutes to hours, diffuse anemia (occasionally megaloblastic), sensory
capillary damage results in hemorrhagic predominant peripheral neuropathy, hepatic
gastroenteritis. transaminase elevation, noncirrhotic portal
 Nausea, vomiting, abdominal pain, and hypertension, and peripheral vascular
watery diarrhea are common. insufficiency. Skin disorders and cancer may
occur (see below), and a growing body of

lOMoARcPSD|29701429
epidemiologic evidence links chronic arsenic and DMA is usually less than 20 mcg/L in
ingestion with an increased risk of hypertension, the absence of recent seafood ingestion.
cardiovascular mortality, diabetes mellitus, and  It should be noted that although
chronic nonmalignant respiratory disease arsenobetaine is excreted unchanged in
1. Skin lesions, which emerge gradually over a the urine, arsenosugars, which are
period of 10 years, typically begin with a abundant in bivalve mollusks and
seaweed, are metabolized in part to DMA.
characteristic pattern of spotted
2. Blood levels are highly variable and are rarely
("raindrop") pigmentation on the torso and
of value in the diagnosis or management in
extremities, followed after several years by patients capable of producing urine.
the development of hyperkeratotic changes  Although whole-blood arsenic, normally
on the palms and soles. less than 5 mcg/L, may be elevated early
 Skin lesions may occur after lower doses in acute intoxication, it may decline
than those causing neuropathy or anemia. rapidly to the normal range despite
 Arsenic-related skin cancer, which persistent elevated urinary arsenic
includes squamous cell carcinoma, excretion and continuing symptoms.
Bowen's disease, and basal cell 3. Elevated concentrations of arsenic in nails or
carcinoma, is characteristically hair (normally less than 1 ppm) may be
multicentric and occurs in nonsun- detectable in certain segmental samples for
exposed areas. ▪ months after urine levels normalize but
should be interpreted cautiously owing to the
2. Cancer. Chronic inhalation increases the risk
possibility of external contamination.
of lung cancer.
B. Other useful laboratory studies include:
 Chronic ingestion is an established cause  CBC with differential and smear for
of cancer of the lung, bladder, and skin. basophilic stippling
Diagnosis  Electrolytes
 Glucose
 usually is based on a history of exposure  BUN and creatinine
combined with a typical pattern of  liver enzymes
multisystemic signs and symptoms.  CPK
 Suspect acute arsenic poisoning in a patient  Urinalysis
with abrupt onset of abdominal pain, nausea,  ECG and ECG monitoring (with particular
attention to the QT interval)
vomiting, watery diarrhea, and hypotension,
 abdominal and chest x-rays.
particularly when followed by an evolving
pattern of delayed cardiac dysfunction, Treatments
pancytopenia, and peripheral neuropathy.
 Metabolic acidosis and elevated CPK may occur A. Emergency and supportive measures:
early in the course of severe cases. 1. Maintain an open airway and assist
 Some arsenic compounds, particularly those of ventilation if necessary (see Airway) ▪
lower solubility, are radiopaque and may be 2. Treat coma (see Coma and stupor), shock
visible on a plain abdominal x-ray. (Anaphylactic and anaphylactoid reactions),
A. Specific levels. In the first 23 days after acute and arrhythmias (Ventricular arrhythmias) if
they occur.
symptomatic poisoning, total 24-hour urinary
 Because of the association of arsenic with
arsenic excretion is typically in excess of several
prolonged QT intervals, avoid quinidine,
thousand micrograms (spot urine greater than
procainamide, and other type Ia
1000 mcg/L) and, depending on the severity of antiarrhythmic agents.
poisoning, may not return to background levels  Phenothiazines should not be given as
(less than 50 mcg in a 24-hour specimen or less antiemetics or antipsychotics because of
than 30 mcg/L in a spot urine) for several weeks. their ability to prolong the QT interval and
Spot urine analyses are usually sufficient for lower the seizure threshold.
diagnostic purposes. 3. Treat hypotension and fluid loss with
aggressive use of intravenous crystalloid
solutions, along with vasopressor agents if
1. Ingestion of seafood, which may contain very needed, to support blood pressure and
large amounts of nontoxic organoarsenicals optimize urine output.
such as arsenobetaine and arsenosugars, can 4. Prolonged inpatient support and observation
"falsely" elevate measurements of total are indicated for patients with significant
urinary arsenic for up to 3 days. acute intoxication, because cardiopulmonary
 Speciation of urinary arsenic by a and neurologic complications may be
laboratory capable of reporting the delayed for several days.
concentration of inorganic arsenic and its  Continuous cardiac monitoring beyond 48
primary human metabolites, hours is warranted in patients with
monomethylarsinic acid (MMA) and persistent symptoms or evidence of toxin-
dimethylarsinic acid (DMA), may related cardiovascular disturbance,
sometimes be helpful: including electrocardiographic
 Background urine concentration of the
sum of urinary inorganic arsenic, MMA,
lOMoARcPSD|29701429
abnormalities, or any degree of  Was once used as antisyphilitic agent and still
congestive heart failure. currently present in some insecticides.
B. Specific drugs and antidotes.  Note: Hair analysis use to document time of
 Treat seriously symptomatic patients with arsenic exposure; Axillary or pubic hair is use to
chelating agents, which have shown document long term exposure to arsenic
therapeutic benefit in animal models of
acute arsenic intoxication when Antidotes:
administered promptly (ie, minutes to  Freshly prepared Iron (III) and Magnesium
hours) after exposure. hydroxide (if still in the GI tract)
 Treatment should not be delayed during  Dimercaprol (aka 2,3-dimercaptopropanol,
the several days often required to obtain British Anti-Lewisite or BAL) via IM injection
specific laboratory confirmation Special tests to determine the presence of Arsenic
1. Unithiol [2,3-dimercaptopropanesulfonic 1. Gutzeit test
acid, DMPS, Dimaval; see Unithiol], a water- 2. Marsh test
soluble analog of dimercaprol (BAL) that can 3. Reinsch test “Lewisite”
be administered intravenously, has the most
favourable pharmacologic profile for
treatment of acute arsenic intoxication. ANTIMONY
 Although published experience is sparse, Is widely used as a hardening agent in soft metal
3-5 mg/kg every 4 hours by slow alloys and alloys of lead; for compounding
intravenous infusion over 20 minutes is a rubber; as a major flame retardant component
suggested starting dose. of plasticsl and as a coloring agent in dyes and
 In the United States, the drug is available varnishes, paints and glazes.
through compounding pharmacists.  Exposure to antimony dusts and fumes may also
2. Dimercaprol (BAL, British anti-Lewisite, 2-3 occur during minning and refining of ores and
dimercaptopropanol; see BAL) is the from the discharge of firearms.
chelating agent of second choice if unithiol is  Organic antimony compounds are used as
not immediately available. antiparasitic drugs.
 The starting dose is 3-5 mg/kg by deep  Foreign or folk remidies may contain antimony
intramuscular injection every 4-6 hours. potassium tartrate (Tartar emetic).
 Lewisite burns to the skin and eyes can be  Compared to arsenic, it is less readily absorbed
treated with topical inunctions of and produces topical irritation
dimercaprol.  More caustic to the skin than arsenic causing
3. Once patients are hemodynamically stable papular eruptions which develop into vesicular
and GI symptoms have subsided, parenteral and pustular sores
chelation may be changed to oral chelation  Exhibits expectorant and nauseant action orally
with either oral unithiol, or oral succimer in small quantities
(DMSA, 2-3 dimercaptosuccinic acid; see  Exposure to Sb dust over a period of years leads
Succimer [DMSA]). to pneumoconiosis; It may also cause cardiac
 A suggested dose of unithiol is 4-8 mg/kg arrhythmias, spontaneous abortion, and
orally every 6 hours. Alternatively, give dermatitis and inability of the blood to clot.
succimer, 7.5 mg/kg orally every 6 hours Mechanism of toxicity
or 10 mg/kg orally every 8 hours.  Compounds of probably act by binding to
4. The therapeutic endpoints of chelation are sulfhydryl groups, enhancing oxidative stress,
poorly defined. and inactivating key enzymes. Ingested
 For chelation instituted to treat antimonial are also corrosive to mucosal
symptomatic acute intoxication, one membranes.
empiric approach would be to continue
treatment (initially parenterally, then Toxic dose
orally) until total urinary arsenic levels are  The lethal oral dose of metallic antimony in rats
less than 500 mcg/24 hours (or spot urine is 100mg/kg body weightl the trivalent and
< 300 mcg/L), levels below those pentavalent oxides are less toxic, with a Lethal
associated with overt symptoms in Dose 50 (LD50) in rats ranging from 3200-
acutely poisoned adults. 4000mg.kg of body weight.
 Alternatively, oral chelation could be  The recommended workplace limit for antimony
continued until total urinary arsenic levels is 0.5mg/m3 as an 8-hour-time-weighted
reach background levels (< 50 mcg/24 average.
hours or spot urine < 30 mcg/L).  The air level considered immediately dangerous
 The value of chelation for treatment of an to life and health (ILDH) is 50mg/m3 .
established neuropathy (or prevention of Clinical presentation (acute ingestion of antimony)
an incipient neuropathy) has not been  causes nausea, vomiting, hemorrhagic gastritis,
proved. and diarrhea ("cholera stibie").
 Hepatitis and renal insufficiency may occur.
Pharmacological Action & Uses:  Death is rare if the patient survives the initial
 Protoplasmic poison gastroenteritis.
 Effective in polycythemia vera (represses the  Cardiac dysrhythmias (including torsade),
bone marrow which overproduces RBC) pancreatitis, and arthralgias have been
associated with the use of the organic
lOMoARcPSD|29701429
antimonial compounds for treatment of metallic salts are used as pigments and
parasitic infections (e.g. leishmaniasis) stabilizers in plastics, and Cd alloys are used in
Clinical presentation (Chronic exposure to antimony soldering and welding and in nickel-cadmium
dust and fumes) batteries.
 in the workplace is the most common type of  Cd solder in water pipes and Cd pigments in
exposure and may result in headache, anorexia, pottery can be sources of contamination of
pneumonitis, peptic ulcers, and dermatitis water and acidic foods.
(antimony spots).  It is a member of volatile metal group
 Sudden death presumably resulting from a
direct cardiotoxic effect has been reported in Mechanism of toxicity
workers exposed to antimony trisulfide.  Inhaled Cd is at least 60 times more toxic than
 Based on evidence of in vitro genotoxicity and the ingested form.
limited rodent carcinogenicity testing, antimony  Fumes and dust may cause delayed chemical
trioxide is a suspected carcinogen. pneumonitis and resultant pulmonary edema
Diagnosis and hemorrhage.
 is based on a history of exposure and typical  Cd is a known human carcinogen (IARC Group
clinical presentation 1).
A. Specific levels.  Ingested Cd is a GI tract irritant.
 Urine antimony levels are normally below  Once absorbed, Cd is bound to metallothionein
2 mcg/L. Serum and whole-blood levels and filtered by the kidney, where renal tubule
are not reliable and are no longer used. damage may occur
 Urine concentrations correlate poorly
with workplace exposure, but exposure to Toxic dose
air concentrations greater than the TLV- A. Inhalation.
TWA will increase urinary levels.  The ACGIH-recommended threshold limit
 Urinary antimony is increased after value (TLV-TWA) for air exposure to Cd
firearm discharge exposure. dusts and fumes, established in 1993, is
 There is no established toxic antimony 0.01 (inhalable fraction) to 0.002
level after stibine exposure. (respirable dusts) mg/m3 as an 8-hour
B. Other useful investigations include: time-weighted average.
 CBC  Exposure to 5 mg/m3 inhaled for 8 hours
 plasma-free haemoglobin may be lethal.
 serum lactate dehydrogenase (LDH)  The level considered immediately
 free haptoglobin hazardous to life or health (IDLH) for Cd
 electrolytes dusts or fumes is 9 mg Cd/m3.
 BUN B. Ingestion.
 Creatinine  Cd salts in solutions of greater than 15
 urinalysis for free haemoglobin mg/L may induce vomiting.
 liver transaminases  The lethal oral dose ranges from 350 to
 bilirubin 8900 mg.
 prothrombin time C. Water
 12-lead ECG. Chest radiography is  The US Environmental Protection Agency
recommended for chronic respiratory has established a safe limit of 0.005 mg/L
exposures. in drinking water.
Treatment Clinical Presentation

 Large-volume intravenous fluid resuscitation may A. Direct contact may cause local skin or eye
be necessary for shock caused by gastroenteritis irritation.
(see Hypotension).  There are no data on dermal absorption
 Electrolyte abnormalities should be corrected, of Cd in humans.
and intensive supportive care may be necessary B. Acute inhalation may cause:
with multiple organ failure.  Cough
Official Compound  Wheezing
1. Antimony potassium tartrate (KSbOC4H4O6)  Headache
 aka Tartar Emetic  fever, and, if severe, chemical
 formerly used as emetic and pneumonitis
expectorant  noncardiogenic pulmonary edema within
 used as anti-schistosomal agent (IV) 12 - 24 hours after exposure.
C. Chronic inhalation at high levels is associated
CADMIUM with lung cancer.
 is found in sulfide ores, along with zinc and lead. D. Acute ingestion of Cd salts causes nausea,
 Exposure is common during the mining and vomiting, abdominal cramps, and diarrhea,
smelting of zinc, copper, and lead. sometimes bloody, within minutes after
 The metallic form of Cd is used in electroplating exposure. Deaths after oral ingestion result from
because of its anticorrosive properties, the shock or acute renal failure.

lOMoARcPSD|29701429
E. Chronic ingestion results In accumulation of Cd Pharmacological Action

in bones, causing painful itai-itai ("ouch-ouch")  Closely resembles zinc in action but is more
disease, and in kidneys, causing renal disease toxic
 Itai-itai disease (“ouch-ouch disease”)  Behaves like mercury systemically and after
o first documented occurrence of absorption, produces death by arresting
mass cadmium poisoning in the respiration;
world due to mining in Toyama o its toxicity results to renal dysfunction with
Prefecture; contracted from proteinuria with slow onset.
drinking water and eating rice
contaminated with cadmium MERCURY
Symptoms:  Is a naturally occurring metal that is mined
 Weak and brittle bones chiefly as HgS in cinnabar ore.
 Spinal and leg pain  It is converted to three primary forms, each with
 Anemia a distinct toxicology:
 Kidney failure  elemental (metallic) mercury (Hgo),
 inorganic mercury salts (eg, mercuric
Diagnosis chloride [HgCl2])
 is based on a history of exposure and the  organic (alkyl and aryl) mercury
presence of respiratory complaints (after (eg,methylmercury).
inhalation) or gastroenteritis (after ingestion).  Approximately one-half to one-third of
A. Specific levels. commercial mercury use is in the manufacture
 Whole-blood Cd levels may confirm the of chlorine and caustic soda, one-half to one
exposure; normal levels are less than 1 third in electrical equipment, and the
mcg/L. remainder in various applications, such as
 Very little Cd is excreted in the urine until dental amalgam, fluorescent lamps, switches,
binding of Cd in the kidney is exceeded thermostats, and artisanal gold production.
and renal damage occurs.  In the United States, mercury use in batteries
 Urine Cd values are normally less than 1 and paints has been discontinued.
mcg/g of creatinine.  Previous use in pharmaceuticals and biocides
 Measures of tubular microproteinuria has declined sharply, although mercuric chloride
(beta-microglobulin, retinolbinding is still used as a stool fixative, and some
protein, albumin, and metallothionein) organomercury compounds (such as
are used to monitor the early and toxic mercurochrome, phenylmercuric acetate, and
effects of Cd on the kidney. thimerosal) are still used as topical antiseptics
B. Other useful laboratory studies include: or preservatives.
 CBC  Some folk medicines contain inorganic mercury
 Electrolytes compounds, and some Latin American and
 Glucose Caribbean communities have used elemental
 BUN mercury in religious or cultural rituals.
 Creatinine  Aquatic organisms can convert inorganic
 arterial blood gases or oximetry mercury into methylmercury, with resulting
 chest x-ray. bioaccumulation in large carnivorous fish such
as swordfish.
o Also called liquid silver or quicksilver with
low boiling point and melting point
o Cinnabar (HgS) is a mineral source of
mercury; aka Aethrop’s mineral
Treatment o Mercury that falls into cracks and difficult
A. A. Emergency and supportive measures to clean places is removed best by covering
1. Inhalation with powdered sulfur, allowing several
 Monitor arterial blood gases and obtain days to for conversion to sulfide then
chest x-ray. vacuumed.
 Observe for at least 6-8 hours and treat o Elemental mercury (Hg 0 ) can be
wheezing and pulmonary edema (see converted chemically or biologically to its
Hypoxia and Bronchospasm) if they occur. toxic form (Hg +,2+ ) and or the methylated
 After significant exposure, it may be or alkyl Hg which will result kidney failure.
necessary to observe for 12 days for o Mercury and its compounds are inherently
delayed-onset noncardiogenic pulmonary toxic
edema.
2. Ingestion Mechanism of toxicity
 Treat fluid loss caused by gastroenteritis  Mercury reacts with sulfhydryl (SH) groups,
with intravenous crystalloid fluids resulting in enzyme inhibition and pathologic
B. Specific drugs and antidotes alteration of cellular membranes.
 There is no evidence that chelation o Elemental mercury and methylmercury
therapy (eg, with BAL, EDTA,or are particularly toxic to the CNS.
penicillamine) is effective, although Metallic mercury vapour is also a
various chelating agents have been used. pulmonary irritant. Methylmercury is

lOMoARcPSD|29701429
associated with neurodevelopmental  Ingestion of 10 to 60 mg/kg may be lethal,

disorders. and chronic daily ingestion of 10 mcg/kg
o Inorganic mercuric salts are corrosive to may be associated with adverse
the skin, eyes, and GI tract and are neurologic and reproductive effects.
nephrotoxic.  The US Environmental Protection Agency
o Inorganic and organic mercury reference dose (RfD), the daily lifetime
compounds may cause contact dose believed to be without potential
dermatitis.
hazard, is 0.1 mcg/kg/day.
Toxic dose
 The RfD was derived from studies of
 The pattern and severity of toxicity are highly
neuropsychologic deficits arising from in
dependent on the form of mercury and the
utero exposure in humans.
route of exposure, mostly because of different
 To minimize neurodevelopmental risk, the
pharmacokinetic profiles.
US EPA and FDA have advised pregnant
 Chronic exposure to any form may result in
women, women who might become
toxicity.
pregnant, nursing mothers, and young
A. Elemental (metallic) mercury is a volatile
children to avoid consumption of fish with
liquid at room temperature.
high levels of mercury (such as swordfish)
 Hgo vapor is absorbed rapidly by the
and to limit consumption of fish and
lungs and distributed to the CNS.
shellfish with lower mercury levels to no
o Airborne exposure to 10 mg/m3 is
more than 12 ounces (two average meals)
considered immediately dangerous to
perweek
life or health (IDLH), and chemical
(www.epa.gov/waterscience/fishadvice/a
pneumonitis may occur at levels in
dvice.html).
excess of 1 mg/m3.
3. Dimethylmercury, a highly toxic synthetic
o In occupational settings, overt signs and
liquid used in analytic chemistry, is well
symptoms of elemental mercury
absorbed through the skin, and cutaneous
intoxication generally have required
exposure to only a few drops has resulted
months to years of sustained daily
in a delayed but fatal encephalopathy.
exposure to airborne mercury levels of
 Causes Minamata disease (acquired through
0.05â€“0.2 mg/m3.
ingestion of contaminated fish, shellfish and sea
o The recommended workplace limit
mammals in Minamata Bay, Japan)
(ACGIH TLV-TWA) is 0.025 mg/m3 as an
8-hour timeweighted average; however, Symptoms of poisoning:
some studies suggest that subclinical
 Initial: burning metallic taste, thirst, sore throat,
effects on the CNS and kidneys may
visual field constriction, hearing loss,
occur below this level.
 Latter: salivation, sore gums, bloody diarrhea,
 Liquid metallic mercury is poorly
severe gastric pain, and cerebral cortex necrosis
absorbed from the GI tract, and acute
ingestion has been associated with
poisoning only in the presence of
abnormal gut motility that markedly
delays normal fecal elimination or after
peritoneal contamination.
B. Inorganic mercuric salts.

 The acute lethal oral dose of mercuric
chloride is approximately 1-4 g. Antidote:
 Severe toxicity and death have been
reported after use of peritoneal lavage  Egg white or milk – to inactivate mercury ions
solutions containing mercuric chloride by coagulation followed by extensive gastric
concentrations of 0.2-0.8%. lavage
C. Organic Mercury  Sodium formaldehyde sulfoxylate – for the
1. Mercury-containing antiseptics such as bichloride
mercurochrome have limited skin  Dimercaprol – agent of choice; given via IM or
penetration; however, in rare cases, such Penicillamine that would mobilize and excrete
as topical application to an infected Hg in the urine.
omphalocele, intoxication has resulted.
 Oral absorption is significant and may also
pose a hazard. Aside from being toxic, Mercury still has Therapeutic
2. Methylmercury is well absorbed after Uses:
inhalation, ingestion, and probably dermal
exposure.

lOMoARcPSD|29701429
 Diuretic – mercurial diuretics bring about sodium

and water diuresis by inhibiting the reabsorption
of sodium
 Antiseptic – mercuric ion is a protein precipitant
 Antisyphilitic – mercury and its salts have been
used in the prophylaxis and treatment of syphilis
(Calomel ointment)
 Cathartic
 Parasiticide and fungicide – used in the treatment
of impetigo and ringworm infections in the form
of Ammoniated Mercury Ointment
NICKEL
 It is was once known as “Old Nick’s copper” or
“Kupfernickel”
 It is use favorably as alloying metal (eg. jewelry)
due to its anticorrosive and hardness property.
 It can be used in nickel-based batteries, catalyst
in the hydrogenation of oil.
 Nickel carbonyl (Ni[CO]4) – used in pertroleum
refining is the most toxic chemical known to
humans.
Alloys:
 Raney Nickel – nickel-aluminum alloy

 German Silver – nickel, zinc, and copper alloy
Exposure and toxicity may cause:
 contact dermatitis
 pulmonary congestion
 inability to oxygenate hemoglobin especially if
lesion in present in liver, kidney, adrenal gland,
and speen.

lOMoARcPSD|29701429
SAS 4: pH & BUFFER SYSTEMS  Osmometry

 technique used for measuring the
pH & HYDRONIUM ION concentration of solute particles that
contribute to the osmotic pressure of the
CONCENTRATION solution
 is a topic of considerable importance in
 Freezing point depression osmometer
analytical chemistry.
 dependent of the changes in ambient
 Polyfunctional acids and bases play important
temperature.
roles in many chemical and biological systems.
 The pH of human blood is controlled to be  Components of a freezing point
within the range of 7.35 to 7.45, primarily by depression osmometer include the
the carbonic acid-bicarbonate buffer system: following:
CO2(g) 1 H2O(l) 8 H2CO3(aq) H2CO3(aq) 1 1. A thermostatically controlled cooling
H2O(l) 8 H3O1(aq) 1 HCO3 2(aq) bath or block maintained at −7 °C.
2. A rapid stir mechanism to initiate
(“seed”) freezing o the sample.
3. A thermistor probe connected to a
circuit to measure the temperature of
the sample.
4. A light-emitting diode (LED) display
that indicates the time course of the
freezing curve and the final result
 Vapor pressure osmometer
 related directly not to a change in vapor
pressure (in millimetres of mercury) but
to the decrease in dew point
temperature of the pure solvent (water)
caused by the decrease in vapor pressure
of the solvent by the solutes.
 Clinical difference of the two:
COLLIGATIVE PROPERTIES  the failure of the former to include in its
 are directly related to the total number of measurement of total osmolality any volatile
solute particles per mass of solvent. solutes present in the serum
 Properties include:
o increased osmotic pressure BLOOD GAS
o lowered vapour pressure  Determination of blood gases also plays an
o increased boiling point important part in the detection of acidbase
o decreased freezing point imbalances
 Determination of gas pressures in expired air or
Note: : The colligative property is based on principle that in blood depends on the application of certain
increasing osmotic pressure when the solute is added to the physical principles according to the following
solvent, the vapor pressure of the solution is lowered below principles:
that of the pure solvent. As a result of the change in vapor  Boyle’s law: The volume of an ideal gas at a
pressure, the boiling point of the solution is raised above and constant temperature varies inversely with the
the freezing point of the solution is lowered below that of the pressure exerted to contain it.
pure solvent. A solution is system compose of one or more  Charles’ (Gay-Lussac’s) law: The volume of an
solute/s and one or more solvent/s. The solute usually exist in ideal gas at a constant pressure varies directly
smaller quantity than that of the solvent with its absolute temperature.
 Avogadro’s hypothesis: Equal volumes of
 Osmotic pressure different ideal gases at the same temperature
 is considered to be of biological important and pressure contain the same number of
 generally governs the movement of solvent molecules.
(water in biological systems) across  Dalton’s law: The total pressure exerted by a
membranes that separate two solutions. mixture of ideal gases is the sum of the partial
 Osmotic concentrations pressure of each of the gases in the mixture.
 can be expressed either through  Henry’s law: The amount of a sparingly soluble
osmolarity or osmolality gas dissolved in a liquid is proportional to the
 Osmolality expresses concentrations relative to partial pressure of the gas over the liquid.
mass of the solvent (1 Osmol/kg H2O)
o is what the clinical laboratory  Total Carbon Dioxide (Bicarbonate)
measures.  Carbon dioxide is colorless and harmless
 Osmolarity expresses concentrations per gas
volume of solution (1 Osmol/L solution).

lOMoARcPSD|29701429
 generally use as respiratory stimulant concentration of hemoglobin in

usually with 507% oxygen the erythrocytes (hypochromic
 Total carbon dioxide is measured in the anemia).
clinical laboratory by: o Decreased FO2Hb haemoglobin
1. acidification of a serum or plasma also occurs as a result of
sample and measurement of carbon poisonings that convert part of the
dioxide released by the process or hemoglobin into the species:
2. alkalinisation and measurement of  carboxyhemoglobin
total bicarbonate. (COHb)
 methods used or total CO2 measurement  methemoglobin (MetHb)
with today’s automated instruments may  sulf-emoglobin (Sul Hb),
be:  cyanmethemoglobin
o electrode based - the amount o which cannot properly bind or
released gaseous CO2 after exchange O2.
acidification is determined by a PCO2 o The affinity of hemoglobin for O2
electrode may depends on the following
o enzymatic methods or CO2 - the actors:
specimen is first alkalinized to convert 1. Temperature
all CO2 and carbonic acid to HCO3- 2. pH
3. PCO2
 Oxygen in Blood 4. concentration of 2,3-
 The total O2 content (ctO2 or diphosphoglycerol (2,3-DPG).
concentration of total oxygen gas) of a  Pulse oxymeter - commonly use to
blood sample is the sum of the continuously monitor saturation factor of
concentrations of hemoglobin-bound O2 oxygen in haemoglobin (SO2Hg) because
and of dissolved O2. It is more reliable.
 At a blood ctO2 of 9 mmol/L, the O2  often serve as a
associated with hemoglobin as surrogate for PO2.
oxyhemoglobin (O2Hb or oxygen gas in
hemoglobin) is 8.86 mmol/L ACID-BASE PHYSIOLOGY
 O2Hb is defined as erythrocyte  Acid-base balance involves in an accounting of
hemoglobin with O2 reversibly bound to the carbonic acid (H2CO3, HCO3, CO3 and CO2)
Fe2+ of its heme group. Each mole of and non-carbonic acids and conjugate bases in
haemoglobin -Fe2+ binds 1 mol of O2 terms of input (intake plus metabolic production)
 Uptake of O2 by the blood in the lungs is and output (excretion plus metabolic conversion)
governed primarily by the PO2 (Partial over a given period of time.
pressure of oxygen gas) of alveolar air and
by the ability of dO2 (dissolved oxygen  Acidemia (Acidosis) is defined as an areterial
gas) to diffuse freely across the alveolar blood pH <7.35
membrane into the blood  Alkalemia (Alkalosis) indicates an arterial blood
o When all haemoglobin is pH >7.45
saturated with O2, a further  Acid-base balance is the homeostatic
increase in the PO2 of alveolar air maintenance of acids and bases within the body
simply increases the concentration to achieve a physiological pH of approximately
of O2 in the arterial blood 7.40
o Decreases in arterial FO2Hb
(fraction of oxygen in hemoglobin) The steps in acid excretion in the kidneys are as
may indicate a low arterial PO2 or follows:
an impaired ability of hemoglobin 1. Through glomerular filtration, sodium salts of
to bind O2. mineral and organic acids are removed from the
o Decreases in PO2 indicate a plasma
reduced ability of O2 to diffuse
from alveolar air into the blood 2. Once transferred from the renal filtrate or
tubular fluid, sodium reacts in the tubule cells
with carbonic acid formed by the carbonic
anhydrase-catalyzed reaction of carbon dioxide
o Decreases in the concentration of and water in a chemical process called the
total haemoglobin can result from sodium-hydrogen exchange:
a decreased number of  Na + H2CO3 NaHCO3 + H
erythrocytes that contain a normal
3. The sodium bicarbonate then return to the
concentration of hemoglobin
plasma, having excreted from the lungs as CO2,
(normochromic anemia) or a
decreased mean cell
lOMoARcPSD|29701429
now the protons enter the tubular fluids, amine groups in proteins (carbamine
forming acids of the anions of the sodium salts. compounds), HCO3 − , and very small quantities
of CO3 2 − ions and carbonic acid (H2CO3). Acid-
 Many pathological conditions are accompanied base disturbances are traditionally classified as
by acid –base and electrolyte disturbances in (1) metabolic acidosis, (2) metabolic alkalosis,
the blood . (3) respiratory acidosis, or (4) respiratory
 Abnormalities in acid-base status of the blood alkalosis. A useful and more logical approach is
are always accompanied by characteristic to realize that an acidosis only occurs as the
changes in electrolyte concentrations in the result of one (or a combination) of three
plasma. mechanisms: (1) increase addition of acid, (2)
 Hydrogen ions cannot accumulate without decrease elimination of acid, and (3) increased
concomitant accumulation of anions (such as, loss of base. Similarly, alkalosis occurs only by
Cl− or lactate), or without exchange or cations (1) increase addition of base, (2) decreased
(such as, K+ or Na+). elimination of base, and (3) increased loss of
acid.
Sodium
 Disorders of Na+ homeostasis can occur because of
excessive loss, gain or retention of Na+ or
because of excessive loss, gain, or retention of
H2O.
 When kidneys are hypoperfused (when renal
volume decreases), the distal tubules, under the
influence of aldosterone reclaim Na+ .
 Water regulation in the kidney occurs from the
distal tubule through the collection duct where
tubular permeability to H2O is under the
influence of antidiuretic hormone (ADH).
 The body’s mechanism for restoring Na+ /H2O
homeostasis is H2O.
Potassium
 Disturbances in potassium homeostasis has
serious consequences.
 Hypokalemia is associated with serious  Conditions Resulting to Metabolic Acidosis:
neuromuscular symptoms, tachycardia that may 1. Methanol ingestion
lead to cardiac arrest. 2. Renal failure
 On the other hand, hyperkalemia causes mental 3. Diabetes (Ketoacidosis)
confusion, flaccid paralysis of the extremities, 4. Paraldehyde Toxicity
bradycardia, severe vascular collapse and 5. Ischemia
cardiac arrest. 6. Lactic acidosis
7. Ethylene glycol ingestion
8. Salicylate intoxication
Chloride 9. Diarrhea (severe)
 In the absence of acid -base disturbances, Cl−
concentrations in plasma generally will follow Note: Laboratory parameter usually shows an
those of Na+ . elevated anion gap and this is often the first
 In respiratory acidosis, it is accompanied by indication of a metabolic acidosis and should be
increase HCO− 3 , is another common cause of assessed in the electrolyte profile of all patients.
decrease Cl− with normal Na+ .
Conditions leading to Metabolic Alkalosis:
 Increase plasma Cl− concentration, similar to 1. Prolonged vomiting
2. Upper duodenal obstruction
increase Na+ concentration, occurs with
3. Prolonged diuretic therapy (loop diuretic)
dehydration, prolonged diarrhea with loss of sodium
4. Cystic fibrosis
bicarbonate, and overtreatment with normal saline 5. Mineralocorticoid (primary and secondary
solutions, which have a Cl− content of 154 mmol/L. hyperaldosteronism, Bilateral adrenal
 It may also be seen in respiratory alkalosis hyperplasia,
because of renal compensation for excreting 6. Glucocorticoid excess (Primary adrenal
HCO−3 . adenoma or Cushing syndrome and disease,
Bicarbonate exogenous cortisol therapy, excessive
 The total carbon dioxide (CO2) content of licorice ingestion, Barterr syndrome
7. High doses of bicarbonate, sodium citrate,
plasma consists of carbon dioxide dissolve in an
antacids, carbenicillin or penicillin
aqueous solution ( CO2), CO3 loosely bound to
lOMoARcPSD|29701429
Conditions leading to Respiratory Acidosis: 1. the PCO2, which is regulate by the lungs
1. Overdose of narcotics and barbiturates
an represents the acid component of the
2. Central nervous system trauma, tremors
carbonic acid /bicarbonate buffer system
and degenerative disorders
2. the concentration of titratable base which
3. Infection in the CNS (encephalitis and
is regulate by the kidneys.
meningitis)
4. Comatose patient secondary to
cerebrovascular accident caused by
intracranial hemorrhage
5. Chronic obstructive disease
6. Pulmonary fibrosis
7. Status asthmaticus (severe)
8. Pulmonary infection
9. Neurological disorders affecting the muscles
in respiration
10. Abdominal distention as in peritonitis and
ascites
11. Extreme obesity
12. Sleep apnea
 Factors Causing Respiratory Alkalosis:
1. Anxiety
2. Gram-negative septicemia
BUFFER SYSTEMS
3. Metabolic encephalopathy
 A buffer is a mixture of a weak acid and a salt of
its conjugate base that resists changes in pH
when a strong acid or base is added to the
4. Meningitis and Encephalitis solution
 Generally, buffers work best at resisting pH
5. Intracranial surgery changes in the interval ±1 pH unit of its pK,
(buffers work best when the ratio of acid /base
6. Severe anemia leading to hypoxia is within the range of 10:1 to 1:10). Buffers are
also more effective at higher concentrations.
7. Overuse of salicylates, catecholamines
 Efficient buffer systems utilized by the body to
and progesterone (increase progesterone
maintain pH are found in:
esp. in 3rd trimester)
1. Bicarbonate/Carbonic acid (HCO3 /
8. Hyperthyroidism H2CO3),in the plasma and kidneys;
 It is the most buffer of plasma.
 Normal bicarbonate/d CO2 ratio is 20:1.
9. Pneumonia  The effectiveness of the bicarbonate buffer is
based on the fact that the lungs are able to
10. Asthma readily dispose of or retain CO2 while the renal
tubules are able to increase or decrease the rate
11. Pulmonary emboli of reclamation of bicarbonate rom the
glomerular filtrate.
12. Congestive heart failure 2. Phosphate Buffer [Monohydrogen
phosphate/dihydrogen phosphate
APPLICATION OF HENDERSON- (HPO4/H2PO4)], in the cells and kidneys;
HASSELBALCH EQUATION  The total concentration of this buffer in both
erythrocytes and plasma accounts for about 5%
 Acids are chemical substances that donate of the nonbicarbonate buffer value of plasma.
protons (H+ ions) in solution  Organic phosphate (2,3-diphosphoglycerate)
 bases are substances that accept protons present in erythrocytes, accounts for about 16%
 The pH of the solution is defined as the negative of the nonbicarbonate buffer value of
logarithm of the hydrogen ion activity (pH= -log erythrocytes.
aH+ ) 3. Plasma Protein and Hemoglobin Buffer
 acids = pk values of < 7.0  Hemoglobin and proteins (esp. albumin),
o the lower the pk, the stronger the account for the greatest portion (>90%) of the
acid is non-bicarbonate buffer value of plasma.
 bases = pk values of > 7.0  It is the most effective system for buffering the
o the higher the pk, the stronger the carbonic acid produced during metabolic
conjugate base is processes.
 pH of plasma may be considered to be a
function of two independent variables:
lOMoARcPSD|29701429
SAS 5: QUANTITATIVE CHEMISTRY (DIFFERENTIATE

METHODS OF DETERMINATION & EXPRESSION OF
CONCENTRATION)
SI UNITS
 volts, hertz, coulombs, and joules, are derived
from these base units
 The liter, the SI unit of volume, is defined as

exactly 1023 m3 . THE MOLE (mol)
 The milliliter is defined as 1026 m3 , or 1 cm3 .  SI unit for the amount of a chemical substance
 always associated with specific microscopic entities
 THE DISTINCTION BETWEEN MASS AND such as atoms, molecules, ions, electrons, other
WEGHT particles, or specified groups of such particles as
 Mass is an invariant measure of the quantity of represented by a chemical formula.
matter in an object  Avogadro’s number = 6.02 x 1023
 A chemical analysis is always based on mass so  M (molar mass) = 1 mole
that the results will not depend on locality
 Weight is the force of attraction between an
object and its surroundings, principally the
earth.
 the weight of an object depends on where you
weigh it
 Weight and mass are related by the familiar
expression w 5 mg where w is the weight of an
object, m is its mass, and g is the acceleration
due to gravity
 A balance is used to compare the mass of an
object with the mass of one or more standard
masses
 Because g affects both unknown and known
equally, the mass of the object is identical to the
standard masses with which it is compared
 Weighing is the process of comparing masses
 Weights the objects of known mass as well as
the results of weighing
 analytical data are based on mass rather than  Molarity (M) is defined as the number of
weight moles of solute per liter of solution
o is a measurement of the moles in the
total volume of the solution
o molarity = moles of solute/liters of
solution

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 Molality (m) is defined as the number of

moles of solute per kilogram of solvent  Milliequivalent weight (mEw
o measurement of the moles in
weight) represents the amount of solute in mg
relationship to the mass of the solvent
equal to 1/1000 th gram of the equivalent weight of
o molality = moles of solute/kilograms of
the substance
solvent
 Normality (N) is defined as the number of  Equivalent weight (Eq weight) is the
mass of one equivalent, that is the mass of a given
mole equivalent s per liter of solution
substance which will combine with or displace a
o relates the amount of solute to the total fixed quantity of another substance.
volume of solution; however, normality
is specifically used for acids and bases.
o normality = number of mole
equivalents/1 L of solution
 Moles (n) is the ratio of grams per

Molecular weight

lOMoARcPSD|29701429
SAS 6: VOLUMETRIC METHOD OF ANALYSIS  ENDPOINT

NEUTRALIZATION REACTION, PRECIPITATION,  Refers to a physical manifestation (e.g. color
COMPLEXATION AND REDOX REACTION change, formation of precipitation, etc.) that
signals that the system reached the equivalence
point
TITRATIONS  INDICATORS
 refers to chemical species added to the analyte
 are based on a reaction between the analyte
to aid in signaling the endpoint of the titration.
and a standard reagent known as the titrant.
 The reaction is of known and reproducible
 BACK TITRATION
stoichiometry.  a titration technique where the analyte is
 The volume, or the mass, of the titrant needed first reacted with excess amount of a first
to react completely with the analyte is titrant to ensure completeness of reaction.
 the excess of the first titrant is neutralized
determined and used to calculate the quantity
by careful addition of a second titrant into
of analyte.
the mixture.
 Quantitatively determine concentration of
unknown solution called titrand/analyte.
 A way of determining acid or base concentration TITRIMETRIC CALCULATIONS (EQUIVALENTS)
in a solution  In titriemteric analysis it is convenient to use
equivalents for calculation purposes.
Results in drug assays are usually expressed in
terms of:
 % w/w
 % w/v
 % v/v
- as described in the official
compendiums
The single most important principle which must
be understood regarding equivalents is that:
 1 equiv of an acid neutralizes exactly 1
equiv of a reducing agent, and vice
versa
 EQUIVALENT (equiv)
 equivalen is the quantity of a substance that is
TITRIMETRIC METHODS chemically equivalent to 1.0079g of hydrogen or
 may be defined as those analytical methods in Hydrogen ions.
which the volume of a solution of known  The term equivalent (equiv) is defined as the
concentration consumed during an analysis is number of gram-equivalents involved in a
taken as a measure of the amount of active quantitative procedure.
constituent in a sample being analysed.  GRAME EQUIVALENT WEIGHT (GEW)
For example:  the gram equivalent of a chemical is defined as
 Hydrochloric acid, is assayed by weighing that weight in grams which is chemically
a sample accurately and carefully adding a equivalent to 1 gram-atom of hydrogen
solution of known concentration of (1.0079).
sodium Hydroxide in the presence of a  In neutralization reactions it is defined as that
suitable indicator until equivalent weight of a substance in grams which
amounts of NaOH and HCl have reacted. 1. contains
 In this procedure: 2. furnishes
HCl – analyte / active constituent (the 3. reacts with directly or indirectly, or
chemical substance being analysed) 4. replaces 1 gram-atom or ion of hydrogen
NaOH – titrant (the solution of known  GRAM-EQUIVALENT WEIGHT (GmEW)
concentration)  defined as GEW/1000
 This term is used quite frequently in titrimetric
 TITRATIONS calculations.
 the act of adding and measuring the volume of  MILLIEQUIVALENT (meq)
titrant used in the assay  used more frequently and is defined as the
 The indicator is usually a chemical which number of gram-miliequivalents involved in
changes color at or every near the end point in a quantitative procedure.
the titration where equivalent quantities of  STANDARD SOLUTION
analyte and titrant have reacted.  a solution of known concentration
(Normality/Molarity) used to react with
 STOICHIOMETRIC POINT/EQUIVALENT POINT analyte or sample in titration
 the theoretical point at which equivalent  these solutions should be stable, and reacts
point at which equivalent amount of each rapidly, completely and selectively with the
have reacted analyte solution

lOMoARcPSD|29701429
 STANDARDIZATION because these substances react more

 The determination of the normality or molarity completely with an analyte than do weak acids
of a solution and bases, and as a result, they produce sharper
 the procedure where a primary standard is used end points.
to react with a secondary solution to determine  Standard solutions of acids are prepared by
concentration diluting concentrated hydrochloric, perchloric, or
 simply verifying the concentration of the sulfuric acid.
standard solution that we use for titration  Nitric acid is seldom used because its oxidizing
 This may be accomplished by the use of another properties offer the potential for undesirable
standard solution known as a secondary side reactions.
standard, or by the use of a carefully weighed  Standard solutions of bases are usually
sample of a substance of known purity which is prepared from solid sodium, potassium, and
termed as a primary standard. occasionally barium hydroxides.
 Primary Standard  Neutralization titrations are widely used to
 Chemical species of high purity and of determine the concentration of acidic or basic
known concentration of a secondary analytes or analytes that can be converted to
standard acids or bases by suitable treatment.
 may also be used in other quantitative  Water is the usual solvent for neutralization
analysis titrations because it is convenient, inexpensive,
 Secondary Standard and nontoxic.
 chemical species whose concentration
is determined by standardization Table 1: List of common indicators and the color they emit
against a primary standard INDICATOR ACID BASE
 serves as the working solution in Malachite green yellow green
conducting titrations and in other Methyl yellow red yellow
analytical work Bromophenol blue yellow blue
Methyl orange pink yellow
Volumetric determination of a sample may be Bromocresol green yellow blue
executed with the use of the following glasswares: Methyl red red/pink yellow
Bromocresol purple yellow Purple
Bromocresol blue yellow blue
Phenol red yellow red
Cresol red yellow red
Thymol blue yellow blue
Phenolpthalein colorless Red/pink
Thymolpthalein colorless blue
RULES FOR THE USE OF INDICATORS:

1. Use 3 drops of indicator test solution for a titration
unless otherwise directed.
2. When a strong acid is titrated with a strong alkali,
or a strong alkali with a strong acid, methyl
orange, methyl red or phenolphthalein may be
used.
3. When a weak acid is titrated with a strong alkali,
TYPES OF VOLUMETRIC TITRATION use phenolphthalein as the indicator.
 NEUTRALIZATION 4. When a weak alklali is titrated with a strong acid,
 neutralization titrations depend on a chemical use methyl red as the indicator.
reaction of the analyte with a standard reagent. 5. A weak alkali should never be titrated with a weak
 different types of acid/base titrations: acid, dince no indicator will give a sharp end point
 titration of a strong acid, such as 6. The appearance of a color is more easily
hydrochloric or sulfuric acid, with a observable that is the disappearance. Therefore,
strong base, such as sodium hydroxide always titrate where possible to the appearance
 titration of a weak acid, such as acetic of a color
or lactic acid, with a strong base
 titration of a weak base, such as sodium
cyanide or sodium salicylate, can also be  PRECIPITATION
titrated with strong acids  In volumetric precipitemetry a class of reaction
 Chemical indicator/Instrumental method is dealt with that require the formation of
 is used to locate the end point, relatively insoluble substances or precipitates to
which we hope is very close to the cause the reactions to go to sufficient
equivalence point completion to be quantitative in nature.
 The standard solutions used in neutralization

titrations are strong acids or strong bases
lOMoARcPSD|29701429
The determination for precipitation reaction end point  In an oxidation/reduction reaction electrons
will be the following: are transferred from one reactant to
1. Cessation of precipitation or the another. An example is the oxidation of
appearance of turidity iron(II) ions by cerium(IV) ions. The reaction
2. Use of internal indicators is described by the equation
3. Instrumental methods (i.e. Potentiometric
Ce4+ + Fe2+  Ce3+ + Fe3+
or amperoemtric)
 In this reaction, an electron is
The indicators for the volumetric precipitation will
transferred from Fe2+ to Ce4+ to form
be as follows with the corresponding end point;
Ce3+ and Fe3+ ions.
1. Ferric ammonium sulphate – appearance of
 Oxidizing agent/Oxidant - A substance
red color marks
that has a strong affinity for electrons,
2. Potassium chromate – red precipitate
such as Ce4+
3. Adsorption indicators
 Reducing agent/Reductant - is a
a) Dichloroflutescein (DCF)
species, such as Fe2+, that donates
b) Erosin Y
electrons to another species.
c) Tetrabromophenolphthalein ethyl
 Oxidation/reduction reactions can be
ester
viewed in a way that is analogous to the
Brønsted-Lowry concept of acid/base
 COMPLEXATION
reactions.
 Historically, the quantitative analysis of
 When an acid donates a proton, it becomes
inorganic products containing metal ions
a conjugate base that is capable of
such as Al, Bi, Ca, Mg, and Zn was
accepting a proton.
performed using gravimetric methods.
 when a reducing agent donates an electron,
 Oxalate-permanganate procedure
it becomes an oxidizing agent/conjugate
 which involved a precipitation
oxidant that can then accept an electron.
technique and titration of a carefully
heated sodium of oxalate ions.
 With the introduction of the analytical
reagent Disodium
ethylenediaminetetraacetate (EDTA), a new
volumetric procedure evolved for metal
determination employing metal ions
indicators in the same manner that pH
indicators are used in acid-base titrations.
 Complex - when a metal ion combines Ared + B0x = A0x + Bred
with a molecule which can donate  Box, the oxidized form of species B, accepts
electrons, the resulting compound is electrons from Ared to form the new reductant,
Bred.
termed as a complex.
 At the same time, reductant Ared, having given
 Chelate - if the combining molecule
up electrons, becomes an oxidizing agent, Aox.
contains two or more groups that  If we know from chemical evidence that the
donate electrons, this complex is equilibrium in Equation lies to the right, we can
called as chelate. state that Box is a better electron acceptor
 EDTA will react with metal ions to from (stronger oxidant) than Aox. Likewise, Ared is a
water soluble, stable complex, or chelate more effective electron donor (better
compound. reductant) than Bred.
 Monovalent ions yield relatively weak or
unstable complexes.
SAS 7: PERCENT PURITY COMPUTATION

 REDOX
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 involving the titration of metal ions with the

reagent disodium ethylenediaminetetraacetate
PERCENT PURITY (a salt of edetic acid, or EDTA).
 determination of the concentration of the analyte  Oxidatio-reduction (redox) titrations
present in the sample.  titrations the indicator action is analogous to the
other types of visual colour titrations.
From Faraday’s law the quantity of material present is  In the immediate vicinity of the end point, the
calculated. indicator undergoes oxidation or reduction,
depending upon whether the titrant is an
oxidizing agent or a reducing agent.
Electrical measurements for titrations:

a. Potentiometric titrations
 involve the measurement of the potential
differencebetween two electrodes of a cell;
b. Conductometric titrations
 the electrical conductance orresistance;
c. Amperometric titrations
 Titration  the electric current passing during the course of the
 process of chemical analysis in which the titration;
quantity of some constituent of a sample is d. Cuolemetric titrations
determined by adding to the measured sample  the total quantity of electricity passed during the
an exactly known quantity of another substance titration.
with which the desired constituent reacts in a
definite, known proportion. In the four titrations just mentioned, except
 Equivalence point coulometric titrations, the end point is indicated
 an exactly equivalent amount of titrant has by a marked change in the electrical quantity
that is being measured. In coulometric
been added to the sample.
titrations, the quantity of electricity required to
 Endpoint carry out a known reaction is measured, and
 The experimental point at which the from Faraday’s law the quantity of material
completion of the reaction is marked by present is calculated.
some signal
 signal can be the colour change of an
indicator or a change in some electrical
property that is measured during the
titration.
 Titration error
 The difference between the end point and
the equivalence point, which is kept as small
as possible by the proper choice of an end-
point signal and a method for detecting
it.
TYPES OF VOLUMETRIC TITRATION

 Acid-base titration/Neutralization
 the indicator is a substance that can exist in
two forms, an acid form and a basic form,
which differ in colour.
 Precipitation titration
 may be illustrated by the example of the
determination of chloride content of a
sample by titration with silver nitrate, which
precipitates the chloride in the form of
silver chloride.
 Another method involves the use of an
adsorption indicator, the indicator action
being based on the formation on the
surface of the precipitate of an adsorbed
layer of silver indicator salt, which forms
only when an excess of silver ion is present.
 Complex-formation titrations
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SAS 8: SPECTROSCOPY
SPECTROSCOPY ELECTROMAGNETIC RADIATION

 The interactions of radiation and matter are the  A form of energy which is transmitted through
subject of the science space at enormous velocities
 can be described as a wave with properties of
wavelength, frequency, velocity and amplitude
 Spectroscopic Analytical Method
 are based on measuring the amount of radiation  Under the visible radiation spectrum:
produced or absorbed by molecular or atomic  Ultraviolet radiation
species of interest.  Infrared
 Electromagnetic Spectrum:  Visible light
o g-ray
o X-ray
o Ultraviolet (UV)
o Visible
o Infrared (IR)
o Microwave
o Radio-frequency (RF)
 further to include techniques in which
electromagnetic radiation is not a part of the
measurement.
o acoustic
o mass
o electron spectroscopy
Figure 1. Electromagnetic Spectrum
 The regions of electromagnetic spectrum that

interact with an analyte can result to several
types of changes which vary from a change of:
o Spin
o Orientation
o Configuration
o Electron distribution
o Nuclear configuration
Type of Quantum Type of Spectroscopy Type of
Change Energy
Level
Change of Spin Nuclear Magnetic Resonance Low energy
(NMR)
Electron Spin Resonance (ESR)
Change of Microwave Low energy
Orientation
Change of Infrared (IR) Low energy
Configuration
Change of electron Visible light Low energy
distribution Ultraviolet (UV) High energy
X-ray High energy
Change of nuclear Gamma ray High energy
configuration
Table 1: Type of Quantum Change, Spectroscopy & Energy Level

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
Absorption measurements can give
both qualitative and quantitative
information about the sample
o Photoluminescence Spectroscopy
 the emission of photons is measured
following absorption
 The most important forms of
photoluminescence for analytical
purposes are fluorescence and
phosphorescence spectroscopy
 Absorption Radiation
 Every molecular species is capable of absorbing
its own characteristic frequencies of
Figure 2. Type of Quantum Change and Type of Spectroscopy electromagnetic radiation
 This process transfers energy to the molecule
and as a result decreases the intensity of the
 Wave Properties incident electromagnetic radiation
 The electric field is represented as a vector  Absorption of radiation attenuates the beam in
whose length is proportional to the field strength accordance to the absorption law (Beer-Lambert
 The x axis in this plot is either: law or Beer’s Law).
o Time as the radiation passes
o A fixed point in space
 Absorption Process
o Distance at a fixed time
 As light traverses a medium containing an
Note: The direction in which the field oscillates is absorbing analyte, the intensity decreases and
perpendicular to the direction in which the radiation the analyte becomes more excited.
propagates  For an analyte solution of a given concentration,
the longer the length of the medium through
which the light passes (path length of light), the
more absorbers are in the path, and the greater
the attenuation.
 Similarly, for a given path length of light, the
higher the concentration of absorbers, the
stronger the attenuation
 Absorbance
 The absorbance, A, of a solution is related to the
transmittance in a logarithmic manner, as the
Figure 3. Wave Nature absorbance of a solution increases, the
transmittance decreases
 Spectroscopic Measurements
 Matter interacting with radiation, wherein a
sample is stimulated in a way by applying energy
in the form of:
o Heat
o electrical energy
o light particles
 Reflection and scattering losses (These losses can be
o chemical reaction. substantial) can occur at the cell walls
 Prior to applying this stimulus to matter, the
analyte is in its lowest energy form or ground
state, and upon the introduction to the said For example, about 8.5% of a beam of yellow light is
stimulus will alter it to higher energy state or lost by reflection when it passes through a glass cell.
excited state. Light can also be scattered in all directions from the
surface of large molecules or particles, such as dust, in
o Emission Spectroscopy
the solvent, and this scattering can cause further
 refers to methods in which the attenuation of the beam as it passes through the
stimulus is heat or electrical energy solution. To compensate for these effects, the power
o Chemiluminescence Spectroscopy of the beam transmitted through a cell containing the
 refers to excitation of the analyte by a analyte solution is compared with one that traverses
chemical reaction an identical cell containing only the solvent, or a
 When the sample is stimulated by applying an reagent blank. An experimental absorbance that
closely approximates the true absorbance for the
external electromagnetic radiation source,
solution is thus obtained.
several processes are possible.
o Absorption Spectroscopy
 we measure the amount of light
absorbed as a function of wavelength

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Components:
 Beer’s Law 1. Spectroscopic Source/Source - must generate a
 According to Beer’s law, absorbance is directly beam of radiation that is sufficiently powerful
proportional to the concentration of the enough to be detected and measured
absorbing species, c, and to the path length, b, of Source Wavelength Type of Spectroscopy
the absorbing medium. Xenon arc lamp 250-600 Molecular
fluorescence
A = abc H2 & D2 lamps 160-380 UV molecular
absorption
A = absorbance Tungsten/Halogen 240-2500 UV/Visible/IR
a = absorptivity (molar absorptive coefficient) lamp molecular absorption
b = length of the cuvette (cm) Tungsten lamp 350-2200 Visible/IR molecular
c = concentration (mol/L) absorption
Nernst glower 400-20,000
Wavelength Color of Light Complementary Nichrome wire 750-20,000 IR molecular
(nm) Absorbed Color absorption
Transmitted Globar 1200-40,000
400-435 Violet Yellow-green
435-480 Blue Yellow 2. Wavelength selector
480-490 Blue-green Orange
 Utilizes monochromators or polychromators to
490-500 Green-blue Red
isolate a specific wavelength in the instrument.
500-560 Green Purple
Examples: grating monochromators, prism
560-580 Yellow-green Violet
monochromators
580-595 Yellow Blue
595-650 Orange Blue-green
650-750 Red Green-blue 3. Sample Container / Cell Compartment (Optical
Materials)
 Optical Materials used in the instrument such as:
o the cell (container for the sample)
 UV/VIS Spectroscopy
o lenses and mirrors
o wavelength-selecting elements
must transmit radiation in the wavelength region
being investigated
 Optical materials such as:
o LiF
o fused silica or quartz
o corex glass
o silicate glass
o NaCl, AgCl, or KBr
can be utilized for particular wavelength ranges
FIGURE 4. UV-VIS SPECTROPHOTOMETER.
 Instrument Components
4. Detector
 a device that identifies, records, or indicates a
change in one of the variables in its environment
FIGURE 6 – MECHANISM HOW WOULD A SPECTROPHOTOMETER DETERMINE
CONCENTRATION.
such as pressure, temperature, or
electromagnetic radiation
 Familiar examples of detectors include:
o Photographic Film - for indicating the
presence of electromagnetic or radioactive
radiation
o Pointer of a balance - for indicating mass
differences
o Mercury level in a thermometer - for
indicating temperature

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o Human eye - converts visible radiation into an

electrical signal that is passed to the brain via FUNCTIONAL GROUPS ABSORPTION PEAKS
a chain of neurons in the optic nerve and Wave # (cm-1) Wavelength
produces vision. O-H Aliphatic & 3600 - 3000 2.8 - 3.3
o Transducer - converts nonelectrical quantities, aromatic
such as light intensity, pH, mass, and NH2 Also secondary & 3600 - 3100 2.8 - 3.2
temperature, into electrical signals that can be tertiary
subsequently amplified, manipulated, and
finally converted into numbers proportional to C-H Aromatic 3150 - 3000 3.2 - 3.3
the magnitude of the original quantity C-H Aliphatic 3000- 2850 3.3 - 3.5
C=N Nitrile 2400 - 2000 4.2 - 4.6
C=C Alkyne 2260 - 2100 4.4 – 4.8
5. Signal Processor & readout
COOR Ester 1750 - 1700 5.7 - 5.9
 is an electronic device that may amplify the
COOH Carboxylic acid 1740 - 1670 5.7 - 6.0
electrical signal from the detector.
 may convert the signal from dc to ac (or the C=O Aldehydes & 1740 - 1660 5.7 - 6.0
reverse), change the phase of the signal, and ketones
filter it to remove unwanted components. CONH2 Amides 1720 – 1640 5.8 – 6.1
 may also perform such mathematical operations C=C Alkenes 1670 – 1610 6.0 – 6.2
on the signal as differentiation, integration, or ɸ-O-R Aromatic 1300 – 1180 7.7 – 8.5
conversion to logarithms R-O-R Aliphatic 1160 - 1060 8.6 – 9.4
 Readout devices:
o Digital meter  MASS SPECTROSCOPY
o Computer monitor - computers are often  A powerful and versatile analytical tool which
used to control various instrumental can be used to determine the identity of an
parameters, to process and store data, to unknown compound, its molecular mass, its
print results and spectra, to compare results elemental composition, and its chemical
with various databases, and to communicate structure.
with other computers and network devices  Atomic Mass Spectrometry
o can determine nearly all the elements
 Fourier Transform Spectroscopy in the periodic table.
 An infrared absorption spectrum, even one for a  Molecular Mass Spectrometry
relatively simple compound, often contains a o is capable of providing information
bewildering array of sharp peaks and minima about the structures of inorganic,
 Peaks useful for the identification of functional organic and biological molecules and
groups are located in the shorter-wavelength about the qualitative and quantitative
region of the infrared (from about 2.5 to 8.5 composition of complex mixtures.
mm),  Mass Spectrometer
 where the positions of the maxima are only o analyte molecules are converted to
slightly affected by the carbon skeleton of the ions by applying energy to them
molecule o The ions formed are separated on
 Identifying functional groups in a molecule is the basis of their mass-to-charge
seldom sufficient to positively identify the ratio (m/z) and directed to a
compound, and the entire spectrum from 2.5 to transducer that converts the
15 mm must be compared with that of known number of ions (abundance) into an
compounds electrical signal.
o The ions of different mass-to-charge
ratios are directed to the transducer
sequentially by scanning or made to
strike a multichannel transducer
simultaneously.
o Mass spectrum - The ion
abundance plotted against mass-to-
charge ratio
o Often, singly charged ions are
produced in the ionization source,
and the mass-to-charge ratio is
shortened to just mass so that the
spectrum is plotted as number of
ions versus mass.

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1. DETERMINATION OF CONCENTRATION OF A
Application: GIVEN SAMPLE USING BEER’S PLOT OR LAW
1. Elucidation of the structure of organic and  According to Beer’s law, absorbance is
biological molecules directly proportional to the concentration
2. *Determination of the molecular mass of of the absorbing species, c, and to the path
peptides, proteins, and oligonucleotides length, b, of the absorbing medium
3. Identification of components in thin-layer and
paper chromatograms A = abc
4. *Determination of amino acid sequences in
A = absorbance
sample of polypeptides and proteins
a = absorptivity (molar absorptive coefficient)
5. Detection and identification of species separated
b = length of the cuvette (cm)
by chromatography and capillary electrophoresis
c = concentration (mol/L)
6. *Identification of drugs of abuse and metabolites
of drugs of abuse in blood, urine, and saliva
 Therefore, we can determine the
7. *Monitoring gases in patient’s breath during
concentration of a given sample using the
surgery
formula, and deriving the concentration
8. *Testing for the presence of drugs in blood in
using the beer’s plot
thoroughbred race horses and in Olympic athletes
� = ��c
9. Dating archaeological specimens
Wherein you need to change the formula
10. Analysis of aerosol particles
so that you can arrive with Concentration
11. Determination of pesticide residues in food
(c) Aab=c
12. Monitoring volatile organic species in water
For example:
supplies
https://www.youtube.com/watch?
v=rllHziqWlgU
 Atomic Spectroscopy
 Quantitative and qualitative detection of
elements in parts per million and parts per
billion concentrations.
 Spectroscopic determination of atomic species
can only be performed on a gaseous medium in
which the individual atoms or elementary ions,
such as Fe, Mg, or Al, are well separated from
one another.
o Atomization - the first step in all atomic
spectroscopic procedures
- a process in which a
sample is volatilized and
decomposed in such a
way as to produce gas-
phase atoms and ions
- The efficiency and
reproducibility of the
atomization step can have
a large influence on the
sensitivity, precision, and
accuracy of the method.
Classification of Atomic Spectroscopic Methods

Atomization Temperature Type of Common
Method Condition Spectroscopy name &
(0C) Abbreviation
Inductive 6,000 – 8,000 Emission Mass
coupled
plasma
Flame 1,700 – 3,150 Absorption
Emission
Fluorescence
Electrothermal 1,200 – 3,000 Absorption
Fluorescence
Direct current 5,000 – Emission
– plasma 10,000
Electric arc 3,000 – 8,000 Emission
Electric spark Varied Emission Mass

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SAS 9: REFRACTOMETRY
 The index of refraction of a chemical substance
is defined as the ratio of the velocity of light in
REFRACTOMETRY air to the velocity of light in the medium, or as
 is a quick and reasonably accurate alternative to the ratio of the sine of the angle of incidence to
chemical analysis for serum total protein when a the sine of the angle of refraction, the index of
rapid estimate is required. refraction may be shown as:
 Temperature affects appreciably the refractive
index of a solution, so refractometers for clinical
use compensate for temperature effects.
 The method cannot be used for urine protein
measurement because of excess solutes in  When light passing obliquely from a less dense
relation to the protein. medium to a more dense medium, it will be
bent so that the angle of refraction (r) will be
less than the angle of incidence (i), thus
showing an expression:
Figure 1. Refractometer (handheld) Figure 2. Refractive Index
 Refractometry
 The index of refraction is a physical constant
frequently made use of in the determination of
the identity and purity of drug products and
biological samples.
 may be used to determine quantitatively the
strength and purity of solutions or the
proportions in which liquids are mixed
 Index of Refreaction Figure 5. Mechanism on how refractive index is measured
 When a ray of monochromatic light passes from
 When the angle of incidence (i) increases, the
one transparent substance to another of
angle of refraction (r) also increases and attains
different optical density, some of the light which
its maximum value (rc) as the angle of incidence
passes into the substance is refracted (bent)
approache 90o , and is termed as the grazing
 The extant direction of refraction are dependent
incidence. The maximum value of refraction is
upon the difference between the densities of the
called critical angle rc, the angle of refraction in
two substances
which the angle equals 90o , which can be seen
o Angle of Incidence (l) - the angle
that there exists a ray of refracted light called
between the ray in the first medium and
critical ray, which makes a boundary defining
perpendicular to the dividing surface,
critical angle.
called the normal
 Refractive indexes have varied values with
o Angle of Refraction (r) - the temperature and wavelength, these variables
corresponding angle in the second must be held constant. The usual temperature is
medium at 25oC .
2. The sine of i and the sine of r are directly  This is usually done by circulating water from a
proportional to the velocity of light in the two suitable constant-temperature device, about the
mediums jacketed prisms.
Table 1. Sample different

Refractive indexes
Figure 4. Hand held Refractometer with its parts

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 Aside from the determination of the Refractive o Next will be the determination of the
index of a sample using a refractometer, it can be concentration of the sample using the refractive
further determined and established with the used index (1.638), using the formula of Linear
of computation. Refer to the sample problem regression
below. y = A + Bx.
1. The speed of light in an unknown medium is o Since this time the variable that is being asked is
measured to be 3.281x109m/s. Determine the the concentration of the sample (x), just derive
refractive index of the medium, and classify the the formula
medium according to the table. A was assayed x = y - A/B
wherein it has an angle of incidence of 60 and
an angle of refraction of 45, give the refractive
index of the sample. A calibration curve was
created, and the results has been established
and showed in the table, Assume the following
data, TASK; give the missing values,
n Concentration
1.0002 10%
1.592 40%
50%
1.638
 So based from the problem given it is asking for

two things. First is the Refractive index (n) of the
sample , if it has a concentration of 50%
 And the Concentration of the sample if it has a
refractive index (n) of 1.638
 So using the Calibration curve placed at the
initial part of the problem, we can now
determine the variables that is being asked,
hoping that the linear regreassion value of the
calculator is near to 1
 Basing on the linear regression of the calibration
curve (DATA 1-3 or data that has x and y values),
we can get a value of; 0.99798246, giving us
that the values of both x and y axis are directly
proportional with each other.
https://www.youtube.com/watch?v=GG3sJYuwAKc
From the Calibration curve you may further determine

the needed variables using the formula
y = A + Bx
y = the Refractive index of the problem
x = represents the concentration of the sample
A&B = is found in your calculators respectively
o For the first Variable being asked (n) wherein

Concentration is 50 %. Since 50 is in percent, so
convert it into decimal place so you may use it
in an operation
y = A + Bx
= (0.831852631) + 0.018169473 (50)
y = 1.7413
So we can give the value of y, so, if the sample
has a concentration of 50%, it has a Refractive
index of 1.7413

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SAS 10: SEPARATION TECHNIQUES (CHROMATOGRAPHY)

 Chromatography is based on the principle
where molecules in mixture applied onto the
CHROMATOGRAPHY surface or into the solid, and fluid stationary
 is an important biophysical technique that enables phase (stable phase) is separating from each
the separation, identification, and purification of other while moving with the aid of a mobile
the components of a mixture for qualitative and phase.
quantitative analysis.  The factors effective on this separation process
 Proteins can be purified based on characteristics include:
such as size and shape, total charge, hydrophobic O molecular characteristics related to
groups present on the surface, and binding adsorption (liquid-solid)
capacity with the stationary phase. O partition (liquid-solid)
 4 separation techniques based on molecular O affinity or differences among their
characteristics and interaction type use
molecular weights
mechanism of:
 Based on this approach three components form
O Ion exchange
the basis of the chromatography technique:
O Surface adsorption O Stationary phase: This phase is always
O Partition composed of a “solid” phase or “a layer
O Size exclusion of a liquid adsorbed on the surface a
 Column chromatography is one of the most solid support”.
common methods of protein purification O Mobile phase: This phase is always
 The purpose of applying chromatography which is composed of “liquid” or a “gaseous
used as a method of quantitative analysis apart component.”
from its separation, is to achive a satisfactory O Separated molecules
separation within a suitable time interval  TYPES
O Chromatography methods based on
partition are very effective on
separation, and identification of small
molecules as amino acids,
carbohydrates, and fatty acids
O However, affinity chromatographies (ie.
ionexchange chromatography) are more
effective in the separation of
macromolecules as nucleic acids, and
proteins.
 Paper chromatography is used in
ANALYSIS SEPARATION the separation of proteins, and in
studies related to protein synthesis
 gas-liquid chromatography is
 Chromatography utilized in the separation of alcohol,
 The process in which a solution of a mixture esther, lipid, and amino groups, and
containing inert materials, drug principles, and observation of enzymatic
impurities is separated into its components interactions,
while moving through a bed of fixed porous  molecular-sieve chromatography is
solid having different reversible affinities for the employed especially for the
substances separated. determination of molecular weights
 Useful means of separating and purifying of proteins
complex and closely related materials which are  Agarose-gel chromatography is
difficult to separate by classical methods based used for the purification of RNA,
on differences in solubility and volatility. DNA particles, and viruses
 Principles: O Stationary phase in chromatography, is
1. Resolution of mixtures a solid phase or a liquid phase coated on
2. Determination of homogeneity the surface of a solid phase.
3. Comparison of substances suspected of O Mobile phase flowing over the
being identical stationary phase is a gaseous or liquid
4. Purification phase
5. Concentration of substance from dilute  If mobile phase is liquid it is termed
solutions as liquid chromatography (LC), and
6. Identification and control of technical if it is gas then it is called gas
products chromatography (GC).
7. Quantitative separation from complex
mixtures
8. Indication of molecular structure TYPES:
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1. COLUMN CHROMATOGRAPHY (CC) or distribution coefficient (K) and may be

 Simplest type, also known as elution expressed mathematically as:
chromatography
 Stationary phase or Adsorbent – purified
siliceous earth, activated ammonia, silica gel
and calcium carbonate
O Wet packed or dry packed C�= represents the lower phase
 Solvent or mobile phase or eluant C = represents the uppercase.
 Product obtained is called eluate  The equation may also be expressed in vice-versa
4. PAPER PARTITION CHROMATOGRAPHY (PC)

 The basic principle of separation is that the
differences in partition coefficients of substances
between two immiscible liquids
 If the solid adsorbent is filter paper (cellulose), the
process is referred to as paper chromatography.
 In this process, the mobile phase, usually an
Figure 2. Column Chromatography set-up organic solvent, moves slowly over the stationary
phase, usually water, which is held in place by the
2. ADSORPTION CHROMATOGRAPHY fibers of the filter paper.
 Also known as Liquid-Solid Chromatography O Under such conditions, different
(LSC) substances move over the paper at
 Separation of mixture through a competitive different rates, depending upon the
process in which the molecules of the mobile relative solubilities in the immiscible
phase compete with analyte molecules for polar solvents, resulting in a separation by
adsorption sites on the adsorbent. partition.
 The interaction between the mobile phase and
adsorbent sites are strong, only a small amount
O Thus, if a solution of several different
of analyte will be adsorbed at any time and the constituents is placed at one end of a
movement of the analyte through an adsorption piece of filter paper saturated with water
column will be relatively rapid and closely follow under equilibrium conditions in a closed
the solvent front. vessel, and an organic solvent is allowed
O Conversely, when interactions between to flow slowly through the paper, the
the mobile phase and the adsorbent are different constituents will move at
weak, greater amounts of analyte will different rates characteristic of each
be adsorbed at a time and the substance and separation occurs.
movement of the analyte through the  The ratio of the distance traveled by the front of
column will be slow the mobile phase, from the point of application of
 The selection of the appropriate upper-phase the test substance, is designated as Rf value of the
liquid requires a polarity scale known as the compound:
eluotropic scale – ranked according to their
order of strength of adsorption
3. PARTITION CHROMATOGRAPHY  The ratio between the distances traveled by a

 Liquid-Liquid Chromatography (LLC), both given compound and a reference substance
mobile and stationary phase are liquids constitutes the Rr value. Both Rf and Rr values
 Separation by LLC is based on Nernst’s law – are characteristic constants for different
two practically immiscible solvents are in compounds and may be used for identification
contact with each other and a substance which purposes
is soluble in each is added, the substance  Three main methods:
distributes itself in such a way that at O Descending
equilibrium and at a given temperature the ratio O Ascending
of the concentrations of the two solutions is a O radial chromatography
constant.
 It is the activity ratio rather than the
concentration ratio which remains constant.
When the ratio concentration expresses a 5. REVERSE PHASE CHROMATOGRAPHY (RPC)
distribution value for a single chemical species,
the constant is designated a partition coefficient
 Based on partition phenomenon

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 Non polar solvent is fixed to the paper or solid

column material as a stationary phase
 Polar solvent is the mobile phase
6. ION –EXCHANGE CHROMATOGRAPHY (IEC) 8. THIN LAYER CHROMATOGRAPHY (TLC)

 Materials used in columns are either cation or  Spotting of a sample of a mixture of
anion resins, these substances are insoluble in components at one end of an adsorbent-coated
water, exchanges cations or anions in solution in glass plate or other suitable support followed by
the mobile phase which comes into contact with the passage of a solvent (developer) through
the active sites of exchange resins. the adsorbent for the purpose of separating the
 Both contain exchangeable functional groups

components of a sample
Advantages over PPC o Requires short time (30
attached to an insoluble resinous matrix
mins or less)
composed of styrene-divinylbenzene polymer
O Requires small amount of the material
 Cationic exchanger are capable of quantitatively O Provides complete separation of
removing alkaloid bases from solution. components in complex mixtures
 Anion exchangers may be used to liberate bases

O Sensitive
Stationary phase is a thin plate of silica gel G (G
from alkaloidal salts passed through the
= gypsum, as binder of the silica)
column.
 A white developed chromatogram is examined
 The bases appear in the eluate and may be under UV radiation after separation
recovered or analyzed using conventional  Benzene or chloroform with 10% ethanol is the
methods best solvent for an exploratory run
 Most colored products do not need a special
color-producing reagent to detect the location
of the spot
 Most components are colorless products
require to be examined under UV radiation to
make spots discernible
 UV sources:
O Short wave (254nm)
O Long wave (360nm)
9. GAS CHROMATOGRAPHY (GC)

 Uses as the mobile phase an inert gas called the
FIGURE 3. ION EXCHANGE CHROMATOGRAPHY carrier gas
 Stationary phase, referred to as the liquid
substrate, consisting of a high-boiling liquid
7. MOLECULAR EXCLUSION which is used to coat granular particles made of
siliceous earth or firebrick
CHROMATOGRAPHY (MEC)
 Also known as gel filtration or gel permeation  These coated particles are housed in a tube
which is made of copper, glass or stainless steel.
chromatography
 A separation procedure in which differential  This tube is called the column, mounted in a
constant-temperature chamber
migration of solute molecules is based on
molecular size. Column materials consist of a
network-like structure of polymer materials
having pores of various sizes which exclude
10. HIGH-PRESSURE LIQUID
some molecules but permit the passage of CHROMATOGRAPHY (HPLC)
other smaller molecules
 Separation using HPLC depend upon the
 Inorganic and organic materials can be applied processes of adsorption, partition, ion-
in gas and liquid chromatography as well as in exchange, and molecular exclusion.
column
 The retention volume is expressed in:  Greater speed, precision and accuracy, and
general ease in the operation of this
chromatographic method
lOMoARcPSD|29701429
 The mobile phase varies from aqueous to non-

aqueous solvents, must be degassed to remove
the formation of bubbles (causes erroneous
reading)
 HPLC utilizes detectors (UV absorbance and

refractive index), monitors the column effluent
continuously as it passes through the column,
and a differential plot (peak) is obtained, often
using AUFS (absorbance units full scale) on the
chromatograms, with their respective refractive
index in one side of the reading
Figure 4. High Pressure Liquid Chromatography
Apparatus
Chromatography technique is a valuable tool for
biochemists, besides it can be applied easily during
studies performed in clinical laboratories For
instance, paper chromatography is used to
determine some types of sugar, and amino acids in bodily fluids
which are associated with hereditary metabolic disorders. Gas
chromatography is used in laboratories to measure steroids,
barbiturates, and lipids. Chromatographic technique is also used in
the separation of vitamins, and proteins.


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CHE 029 Notes(Completed)

Analytical Chemistry (Qualitative and Quantitative Chemistry) (Southwestern University

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SAS 1: REVIEW ON BASIC CHEMISTRY AND

Date: 12-01-22 Subject: CHE 029 (Analytical Chemistry) - Lecture

4. Mixture- is a mass if ingredients with a variable 3. Metamorphous - the same

Ex. Potassium permanganate &

Date: 12-01-22 Subject: CHE 029 (Analytical Chemistry) - Lecture

Rules in naming acids:  atom has a small, dense nucleus that

Date: 12-01-22 Subject: CHE 029 (Analytical Chemistry) - Lecture

THE ROLE OF ANALYTICAL CHEMISTRY A TYPICAL QUANTITATIVE ANALYSIS

Date: 12-01-22 Subject: CHE 029 (Analytical Chemistry) - Lecture

ion to be determined and reveals

 FLUORESCENT POLARIZATION IMMUNOASSAY  “Dietary inorganic macro-mineral”

SODIUM (Normal values: 135-147 mEg/L)  Potassium supplements should not be

Date: 12-01-22 Subject: CHE 029 (Analytical Chemistry) - Lecture

Date: 12-01-22 Subject: CHE 029 (Analytical Chemistry) - Lecture

Pharmacological Action: Iron Preparations:

Date: 12-01-22 Subject: CHE 029 (Analytical Chemistry) - Lecture

2. When should I be looking out for electrolyte SAS 3: TOXIC METALS

 a technique which involves the

 Symptoms do not occur immediately but are

Date: 12-01-22 Subject: CHE 029 (Analytical Chemistry) - Lecture

three times per day.Prussian blue particles of silicon and transport

a. The multisystem toxicity of lead is mediated by 1. Acute symptomatic intoxication is rare

constipation, or (less commonly) specific environmental exposure. Levels

o Asymptomatic adults  Phenylarsenic compounds are used as feed

C. The chemical warfare agent lewisite (dichloro [2-

Date: 12-01-22 Subject: CHE 029 (Analytical Chemistry) - Lecture

Treatment Clinical Presentation

Date: 12-01-22 Subject: CHE 029 (Analytical Chemistry) - Lecture

E. Chronic ingestion results In accumulation of Cd Pharmacological Action

Date: 12-01-22 Subject: CHE 029 (Analytical Chemistry) - Lecture

associated with neurodevelopmental  Ingestion of 10 to 60 mg/kg may be lethal,

B. Inorganic mercuric salts.

Date: 12-01-22 Subject: CHE 029 (Analytical Chemistry) - Lecture

 Diuretic – mercurial diuretics bring about sodium

 Raney Nickel – nickel-aluminum alloy

Exposure and toxicity may cause:

Date: 12-01-22 Subject: CHE 029 (Analytical Chemistry) - Lecture

SAS 4: pH & BUFFER SYSTEMS  Osmometry

Date: 12-01-22 Subject: CHE 029 (Analytical Chemistry) - Lecture

 generally use as respiratory stimulant concentration of hemoglobin in

 Factors Causing Respiratory Alkalosis:

SAS 5: QUANTITATIVE CHEMISTRY (DIFFERENTIATE

 The liter, the SI unit of volume, is defined as

Date: 12-01-22 Subject: CHE 029 (Analytical Chemistry) - Lecture

 Molality (m) is defined as the number of

 Moles (n) is the ratio of grams per

Date: 12-01-22 Subject: CHE 029 (Analytical Chemistry) - Lecture

SAS 6: VOLUMETRIC METHOD OF ANALYSIS  ENDPOINT

Date: 12-01-22 Subject: CHE 029 (Analytical Chemistry) - Lecture

 STANDARDIZATION because these substances react more

RULES FOR THE USE OF INDICATORS:

 The standard solutions used in neutralization

SAS 7: PERCENT PURITY COMPUTATION

 involving the titration of metal ions with the

Electrical measurements for titrations:

TYPES OF VOLUMETRIC TITRATION

SPECTROSCOPY ELECTROMAGNETIC RADIATION

Figure 1. Electromagnetic Spectrum