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    The document discusses important units of measurement used in analytical chemistry including SI units, mass vs weight, the mole unit, molarity and other concentration units, density, and stoichiometric calculations. Key concepts covered include the distinction between mass and weight, defining the mole and calculating amounts of substances in moles, methods for expressing solution concentration such as molarity and percentage, and using balanced chemical equations to relate amounts of reactants and products.

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    The document discusses important units of measurement used in analytical chemistry including SI units, mass vs weight, the mole unit, molarity and other concentration units, density, and stoichiometric calculations. Key concepts covered include the distinction between mass and weight, defining the mole and calculating amounts of substances in moles, methods for expressing solution concentration such as molarity and percentage, and using balanced chemical equations to relate amounts of reactants and products.

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    The document discusses important units of measurement used in analytical chemistry including SI units, mass vs weight, the mole unit, molarity and other concentration units, density, and stoichiometric calculations. Key concepts covered include the distinction between mass and weight, defining the mole and calculating amounts of substances in moles, methods for expressing solution concentration such as molarity and percentage, and using balanced chemical equations to relate amounts of reactants and products.

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    The document discusses important units of measurement used in analytical chemistry including SI units, mass vs weight, the mole unit, molarity and other concentration units, density, and stoichiometric calculations. Key concepts covered include the distinction between mass and weight, defining the mole and calculating amounts of substances in moles, methods for expressing solution concentration such as molarity and percentage, and using balanced chemical equations to relate amounts of reactants and products.

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    of 31

    Chapter 4:

    Calculations Used in Analytical Chemistry


    4A Some important units of measurement
    4A-1 SI Units
    SI is the acronym for the French “Système International d’Unités.”
    The International System of Units (SI) is based on 7 fundamental base units.
    Numerous other useful units, such as
    volts, hertz, coulombs, and joules, are derived
    from these base units.
    To express small or large measured
    quantities in terms of a few simple digits,
    pre-fixes are used with these base units and
    other derived units.
    The ångstrom unit Å is a non-SI unit of length widely used to express the
    wavelength of very short radiation such as X-rays (1 Å = 0.1 nm).

    Thus, typical X-radiation lies in the range of 0.1 to 10 Å.

    Metric units of kilograms (kg), grams (g), milligrams (mg), or micrograms (µg)
    are used in the SI system.

    Volumes of liquids are measured in units of liters (L), milliliters (mL),


    microliters (µL), and sometimes nanoliters (nL).

    The liter, the SI unit of volume, is defined as exactly 10-3 m3. The
    milliliter is defined as 10-6 m3, or 1 cm3.
    4A-2 The Distinction Between Mass and Weight
    Mass is an invariant measure of the quantity of matter in an object.
    1. Weight is the force of attraction between an object and its surroundings,
    principally the earth. Because gravitational attraction varies with geographical
    location, the weight of an object depen
    2. Weight and mass are related by the familiar expression

    w  mg

    w is the weight of an object,


    m is its mass, and
    g is the acceleration due to gravity.

    Analytical data are based on mass rather than weight.


    A balance is used to compare the mass of an object with the mass of one or
    more standard masses.
    g affects both unknown and known equally, hence, the mass of the object is
    identical to the standard masses with which it is compared.
    4A-3 The Mole

     The mole (abbreviated mol) is the SI unit for the amount of a chemical
    substance.

     It is always associated with specific microscopic entities such as atoms,


    molecules, ions, electrons, other particles, or specified groups of such
    particles as represented by a chemical formula.

     It is the amount of the specified substance that contains the same


    number of particles as the number of carbon atoms in exactly 12 grams of
    12C.

     This is Avogadro’s number NA= 6.022 x 1023.

     The molar mass M of a substance is the mass in grams of 1 mole of that


    substance.
    The number of moles nX of a species X of molar mass MX is given by

    mx
    amountX  nx 
    Mx

    The molar mass of glucose is:


    4A-4 The Millimole
    1 millimole = 1/1000 of a mole 1 millimolar mass (mM) = 1/1000 of the molar mass.
    1 mmol = 10-3 mol, and 103 mmol = 1 mol

    4A-5 Calculating the Amount of a Substance in Moles or Millimoles


    4B Solutions and their concentrations
    4B-1 Concentration of Solutions
    The molar concentration cx of a solution of a solute species X is the number
    of moles of that species that is contained in 1 liter of the solution (not 1 L of
    the solvent).
    molesofsolute
    nx molarconcentration 
    cx  volumeinliters
    V
    n, number of moles of solute and V, the volume of solution

    The unit of molar concentration is molar, symbolized by M, which has the


    dimensions of mol/L, or mol L-1.
    Molar concentration is also the number of millimoles of solute per milliliter
    of solution.
    There are two ways of expressing molar concentration:

    Molar analytical concentration is the total number of moles of a solute,


    regardless of its chemical state, in 1 L of solution. The molar analytical
    concentration describes how a solution of a given concentration can be
    prepared.

    The molar equilibrium concentration, or just equilibrium concentration,


    refers to the molar concentration of a particular species in a solution at
    equilibrium.

    To specify the molar equilibrium concentration of a species, it is


    necessary to know how the solute behaves when it is dissolved in a
    solvent.
    They are usually symbolized by placing square brackets around the
    chemical formula for the species. Ex., [H2SO4] = 0.00 M; [H+] = 1.01 M.
    The IUPAC recommends the general term “concentration” to express the
    composition of a solution with respect to its volume, with four sub
    terms: amount concentration, mass concentration, volume
    concentration, and number concentration.

    Molar concentration, molar analytical concentration, and molar


    equilibrium concentration are all amount concentrations by this
    definition.

    The molar analytical concentration of H2SO4 is given by


    cH2SO4 = [SO4-2] + [HSO42]
    because SO4-2 and HSO4 -2 are the only two sulfate-containing species in
    the solution.
    The molar equilibrium concentrations are [SO4-2] and [HSO4 -2].
    Percent Concentration
    weightsolu te
    weightperc ent ( w / w)   100%
    weightsolu tion

    volumesolute
    volumepercent (v / v)   100%
    volumesolution

    weightsolu te, g
    weight / volumepercent ( w / v)   100%
    volumesolution , mL
    In IUPAC terminology, weight percent is mass concentration and volume
    percent is volume concentration.
    Weight percent is often used to express the concentration of commercial
    aqueous reagents. Volume percent is commonly used to specify the
    concentration of a solution prepared by diluting a pure liquid compound
    with another liquid.
    Weight or volume percent is often used to indicate the composition of
    dilute aqueous solutions of solid reagents.
    Parts per million and parts per billion

    In IUPAC terminology, parts per billion, parts per million, and parts per
    thousand are mass concentrations.

    For very dilute solutions, parts per million (ppm) is a convenient way to
    express concentration:

    massofsolute

    c ppm massofsolution  10 6
    ppm

    For even more dilute solutions, 109 ppb rather than 106 ppm is used in
    the previous equation to give the results in parts per billion (ppb).

    The term parts per thousand (ppt) is also used, especially in


    oceanography.
    Solution-Diluent Volume Ratios
    The composition of a dilute solution is sometimes specified in terms of the
    volume of a more concentrated solution and the volume of solvent used in
    diluting it.
    Thus, a 1:4 HCl solution contains four volumes of water for each volume of
    concentrated hydrochloric acid.
    This method of notation is frequently ambiguous.

    p-Functions
    The concentration of a species is expressed as its p-function, or p-value. The
    best-known p-function is pH, which is the negative logarithm of [H+].
    The p-value is the negative logarithm (to the base 10) of the molar
    concentration of that species. Thus, for the species X,

    pX = - log [X]
    Density and Specific Gravity of Solutions
    Density expresses the mass of a substance per unit volume.
    In SI units, density is expressed in units of kg/L or alternatively g/mL.
    Specific gravity is the ratio of the mass of a substance to the mass of an equal
    volume of water.
    Specific gravity is dimensionless and so is not tied to any particular system of
    unit
    Since the density of water is approximately 1.00 g/mL, we use density and
    specific gravity interchangeably.
    Figure 4-1 Label from a bottle of reagent-grade hydrochloric acid.
    The specific gravity of the acid over the temperature range of 60° to 80°F
    is specified on the label.
    Vconcd  cconcd  Vdil  cdil

    The two terms on the left are the volume and molar concentration of a
    concentrated solution that is being used to prepare a diluted solution having
    the volume and concentration given by the corresponding terms on the right.

    This equation is based on the fact that the number of moles of solute in the
    diluted solution must equal the number of moles in the concentrated
    reagent.

    This equation can be used with L and mol/L or mL and mmol/mL.


    4C Chemical stoichiometry
    Stoichiometry is the quantitative relationship among the amounts of reacting
    chemical species.
    The stoichiometry of a reaction is the relationship among the number of
    moles of reactants and products as represented by a balanced chemical
    equation.

    Empirical Formulas and Molecular Formulas


    An empirical formula gives the simplest whole number ratio of atoms in a
    chemical compound.
    A molecular formula specifies the number of atoms in a molecule.
    One or more substances may have the same empirical formula but different
    molecular formulas. A structural formula provides additional information.

    Ex., the chemically different ethanol and dimethyl ether share the same
    molecular formula C2H6O. Their structural formulas, C2H5OH and CH3OCH3,
    reveal structural differences between these compounds that are not shown in
    their common molecular formula.
    4C-2 Stoichiometric Calculations

    A balanced chemical equation gives the combining ratios, or stoichiometry—in


    units of moles—of reacting substances and their products. Therefore, the
    equation

    2NaI(aq) + Pb(NO3)2(aq) PbI2(s) + 2NaNO3(aq)

    indicates that 2 moles of aqueous sodium iodide combine with 1 mole of


    aqueous lead nitrate to produce 1 mole of solid lead iodide and 2 moles of
    aqueous sodium nitrate.
    Figure 4-2 Flow diagram for making stoichiometric calculations.

    (1) When the mass of a reactant or product is given, the mass is first
    converted to the number of moles, using the molar mass.

    (2) The stoichiometric ratio given by the chemical equation for the
    reaction is then used to find the number of moles of another
    reactant that combines with the original substance or the number of
    moles of product that forms.

    (1) Finally, the mass of the other reactant or the product is computed
    from its molar mass.
    Suggested Problems
    • 4.1, 4.4, 4.7-4.15 (odd)

    • 4.17 (odd), 4.20 (odd), 4.23, 4.31, 4.35, 4-39

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