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    Lecture 5

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    Lecture 5

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    of 32

    Empirical Formulas

    Empirical Formulas vs Molecular Formulas


    Molecular Formula: The exact number of atoms of each element that is
    combined (for example, glucose: C6H12O6)

    Empirical Formula: The simplest ratio of atoms of each element in a


    particular compound (for example, glucose: C1H2O1)

    The relationship between molecular formula and empirical formula:


    The molecular formula is equal to the empirical formula times some
    integer, n, where n = 1, 2, 3 …
    Why do we distinguish between molecular formulas and empirical ones?
    Two separate experiments are often needed to evaluate the molecular
    formula
    A brief review :
    Calculating the Chemical Composition of Substances by Relative Mass
    Consider the substance: NaCl
    What % by mass of NaCl is sodium?
    Na: 23 g/mol
    Cl: 35.5 g/mol
    NaCl: 58.5 g/mol
    Na: 23g/58.5 =
    0.393
    Cl: 35.5/58.5 =
    0.607
    0.393+0.607 = 1.0
    Empirical Formulas

    Consider glucose, C6H12O6: How was the molecular formula of glucose


    determined?

    Combustion of organic compounds:


    Most organic compounds when burned in an excess of oxygen form CO2
    and H2O quantitatively.
    C6H12O6 + O2 = CO2 + H2O
    C6H12O6 + 6O2 = 6CO2 + 6H2O
    When 1.0 g glucose is burned it gives rise to 1.467 g of CO2 and 0.6 g H2O
    Can we determine the empirical formula of glucose from this information?
    Before beginning we need to know one more thing: the elements present in glucose –
    C, H, O.
    If all of the carbon in CO2 comes from the carbon in glucose, how much of the 1.467
    g of CO2 isolated is due to the mass of carbon?
    Since we know the composition of CO2, we can determine this exactly;
    In one mol of CO2, we have 12 g of C combined with 32 g of O2
    The fractional mass due to C in CO2 is? 12g/(12 + 32) = 0.2727
    1.467 g * 0.2727 = 0.400 g C in 1.0 g of glucose
    In H2O 2 gH/18 g/mol = 0.111
    Similarly for hydrogen: 0.111 * 0.6g = 0.0666 g H
    When 1.0 g glucose is burned it gives rise to 1.467 g of CO2 and 0.6 g H2O
    C6H12O6 + 6O2 = 6CO2 + 6H2O
    0.400 g C + 0.0666 g H = 0.4666 g accounted for,
    Therefore, the remainder must be due to oxygen
    1.0g – 0.466g = 0.534 g oxygen
    0.40 g C
    0.0666 g H
    0.534 g O
    0.40 g C/12 g/mol = 0.033 mol
    0.066 g H/1 g/mol = 0.066 mol
    0.534 g O/16 g/mol = 0.033 mol
    The ratio of C: H: O atoms in glucose is 1: 2: 1
    The ratio of atoms in glucose (empirical formula) must be C1H2O1

    Unless we know the molecular weight of glucose we cannot proceed any


    further.

    Numerous methods have been developed over the years to measure


    molecular weight.
    Mass spectrometry, Melting point depression, …
    Sample → Sample+ → mass/charge is analyzed

    Mass Spectrum
    The ratio of atoms in glucose (empirical formula) must be C1H2O1

    If we assume a molecular weight of 180 g /mol obtained by mass


    spectrometry
    C1H2O1 = (12 + 2 +16) = 30 g/mol
    180/30 = 6
    Molecular formula = C6H12O6

    Other methods of determining molecular weights include:


    Freezing point depression; Boiling point elevation, Osmotic pressure;
    Titration
    red: oxygen
    grey: carbon
    white: hydrogen
    In Summary
    burn it in xs O2

    To determine the
    molecular formula,
    you need to
    determine the
    molecular weight
    Solutions

    Solute: substance present is the smallest amount


    Solvent: the most abundant substance present

    Define molarity (M) as: mols of solute /liter of solution


    What is the molarity of water?
    How do we calculate it?
    How many grams of H2O in 1000 mL?
    1000 g
    How many mols in 1000g?
    1000g/18 g/mol = 55.5 M
    The molarity of concentrated pure sulfuric acid is 18 M. What is the
    density of sulfuric acid?
    g MW of H2SO4 = 98 g/mol
    One liter of sulfuric acid contains 18 mol.
    How many grams?
    18 M x 98 g /mol = 1764g/1000 mL = 1.764 g/mL
    NaOH 25—
    - Acid-Base Titrations
    -
    30—
    -
    -
    35—
    - 25 mL
    -

    H2SO4
    Acid-Base Titrations

    Suppose we had a solution of NaOH and we wanted to determine its


    concentration in mols/L (M)

    A titration is often performed to achieve this goal. Suppose we had


    available to us a solution of H2SO4 with a known concentration. Lets say
    the concentration of sulfuric acid was 0.1 M. Now suppose we use a
    volumetric flask designed to deliver exactly 25 mL of solution. If we
    placed 25 mL of this sulfuric acid solution in a flask, how many mols of
    H2SO4 would we have in the flask?
    0.1 mol/L * 0.025 L = 0.0025 mol H2SO4
    H2SO4 + NaOH → Na2SO4 +H2O

    First let’s balance the equation


    H2SO4 + 2NaOH → Na2SO4 + 2H2O
    How can we determine when the reaction is complete?

    Acid base indicators: usually weak organic acids that have a neutral
    and ionic form with very different but intense colors. Phenolphthalein
    is such a substance; in solutions that are acidic or neutral, is completely
    colorless. In mildly basic conditions it is converted to a red form whose
    intensity is very strong. By using a very little amount of this substance,
    it is possible to identify the point at which the solution switches from
    being slightly acidic to one becoming slightly basic.
    Suppose in our titration we find that it takes 25.0 mL of our base to make
    the phenolphthalein change to a pink color. What is the concentration of
    our base?
    H2SO4 + 2NaOH → Na2SO4 + 2H2O

    1 mol of H2SO4 neutralizes 2 mol of NaOH


    In the flask we added 0.025 L*0.1M H2SO4 = 0.0025 mol
    0.0025 mol of H2SO4 must neutralize 0.005 mol of NaOH
    That 0.005 mol of NaOH must have been present in 0.025 L of NaOH
    solution
    0.005 mol/0.025L = 0.2 mol/L = 0.2 M NaOH
    Suppose we want to prepare 250 mL of a 0.1 M solution of AgNO3. How
    could we do this
    a: using solid AgNO3?

    A drop of a dilute solution of AgNO3 has been used on new born babies
    at birth to prevent contraction of gonorrhea from the mother.
    Suppose we want to prepare 250 mL of a 0.1 M solution of AgNO3. How
    could we do this
    a: using solid AgNO3?
    Molecular weight of AgNO3?
    Ag = 107.9
    N =14
    O = 16
    AgNO3 =107.9+14+3*16 = 169.9 g/mol
    250 mL = 0.25 L; 0.25 L x0.1 M = 0.025 mol AgNO3
    0.025 mol AgNO3 x 169.9 g/mol = 4.25 g
    dissolve 4.25 g in enough H2O to form 250 mL of solution

    b: using a solution of 1.0 M AgNO3?

    0.25 L x0.1 M = 0.025 mol AgNO3 (V1 x M1 = mol1)


    0.025 mol = 1.0 M2x V2; V = 0.025 L or 25 mL diluted to 250
    mL
    V 1 M 1 = V2 M 2
    Practice Problems
    NaN3 has been used in automobile air bags. When heated to 300 °C it
    basically explodes according to the following reaction:
    NaN3 → Na + N2
    If 1 mole of N2 gas at 1 atm pressure and room temperature occupies
    27 L, how many liters of gas can be formed by heating 38.5 g of NaN3
    What’s the first thing we need to do?
    2NaN3 → 2Na + 3N2 ; NaN3 → Na + 1.5 N2
    gMW of NaN3: 23+ 3*14 = 65 g/mol
    38.5 g/65 g/mol = 0.59 mol NaN3
    How many mol of N2 will be formed?
    1.5 mol of N2/mol of NaN3; 3/2x0.59 mol = 0.89 mol N2
    * 27 L/mol x 0.89 mol = 24.0 L
    Cisplatin, a compound used in the treatment of certain cancers, is
    prepared by reacting ammonia with potassium tetrachloroplatinate:
    2 NH3 + K2PtCl4 = 2 KCl + Pt(NH3)2Cl2
    How many grams of Cisplatin are formed from 55.8 g of K2PtCl4 and
    35.6 g NH3 if the reaction takes place in 95% yield based on the limiting
    reagent.
    K2PtCl4 mw = 2x 39.1 +195.1 +4x 35.5; gmw = 415.3 g / mol
    NH3 = 14 + 3; gmw = 17 g / mol
    Pt(NH3)2Cl2 gmw = 195.1 + 2x 17 + 2x 35.5 = 300.1 g / mol
    mol of K2PtCl4: 55.8 g /415.3 g /mol = 0.134 mol;
    mol of NH3: 35.6 g / 17 g/mol = 2.09 mol;
    K2PtCl4 is the limiting reagent
    0.95x 300.1 g/mol x 0.134 mol = 38.2 g Pt(NH3)2Cl2
    Copper reacts with concentrated nitric acid in the following manner:
    Cu + 4 HNO3 = Cu(NO3)2 + 2NO2 + 2H2O
    If an old copper penny ( 3.045 g) is completely dissolved in nitric acid
    and the solution diluted to 50 mL with water, what is the molarity of the
    Cu(NO3)2?
    Cu: gmw = 63.5 g/mol
    Cu: 3.045 g/63.5 = 0.048 mol
    mol Cu consumed = mol of Cu(NO3)2 formed
    Cu(NO3)2 = 0.048 mol/ 0.050 L
    The solution is = 0.96 M Cu(NO3)2

    cunacid
    Balance the following:
    Reaction of ammonia with iodine:

    NH3 + I2 → NI3 + HI
    NH3 + 3I2 → NI3 + 3HI
    When nitrogen triiodide is agitated, the following occurs:
    NI3 → N2 + I2
    2 NI3 → N2 +3 I2

    NI3.mov
    Let’s balance the following reactions:

    1. NaHCO3 + H2SO4 = Na2SO4 + H2O + CO2


    2 NaHCO3 + H2SO4 = Na2SO4 + 2 H2O + 2 CO2

    2. Pb(NO3)2 + H2SO4 = PbSO4 + HNO3

    Pb(NO3)2 + H2SO4 = PbSO4 + 2 HNO3

    3. C2H5OH + H2SO4 = C4H10O + H2O + H2SO4

    2 C2H5OH + H2SO4 = C4H10O + H2O + H2SO4

    2 C2H5OH + H2SO4 (conc) = C4H10O + H2O + H2SO4 (dilute)

    4. C12H22O11 + H2SO4 (conc) = cca3 formC1


    KMnO4 reacts with oxalic acid in dilute sulfuric acid as follows:
    2KMnO4 + 5H2C2O4 + 3H2SO4 = 2 MnSO4+10 CO2+ 8 H2O + K2SO4
    How many mL of a 0.25 M KMnO4 solution are needed to react
    completely with 3.225 g of oxalic acid?
    What’s the limiting reagent?
    H2C2O4 (OA)
    0.4KMnO4+ H2C2O4+0.6H2SO4=0.4 MnSO4+2CO2+1.6 H2O+0.2K2SO4

    H2C2O4 : mw = 2 +24+64 ; gmw = 90 g/mol


    mol H2C2O4 = 3.225 g/90 g/mol; mol = 0.036
    the amount of KMnO4 needed is 0.036 mol x 0.4 = 0.014 mol

    V x M = mol; V = 0.014mol KMnO4 /0.25 mol/L;


    V = 0.057 L or 57 mL
    The empirical formula of benzoic acid is C7H6O2

    A sample of benzoic acid, 0.122 g, required 10.0 mL of a 0.1M


    solution of NaOH to reach a phenolphthalein endpoint. What is
    the likely molecular weight of benzoic acid

    0.1M NaOH * 0.01L = 0.001 mol of NaOH


    0.122g/MW(benzoic acid) = 0.001
    Assuming that benzoic acid is a monoprotic acid (has only one
    acidic H)
    MW = 0.122/0.001 = 122
    MW (C7H6O2) = 7*12 +6*1+32 = 122
    Empirical formula = molecular formula
    What are the formulas of the following compounds?

    1. sodium phosphate
    2. magnesium sulfate
    3. aluminum chloride
    4. zinc II chloride
    5. iron III bromide
    6. calcium carbonate
    Name the following

    1. Li2S
    2. BCl3
    3. NaHCO3
    4. KCLO4
    5. NaNO3
    6. Li3N
    Elements A and B form two compounds. The ratio (mass
    A)/(mass B) for compound 1 is 2 and ratio (mass A)/(mass B)
    for compound 2 is 0.666. If compound 1 has the chemical
    formula AB, what is the chemical formula for compound 2?

    A/B = 200/100
    Since the ratio of A to B is smaller for compound 2, the
    ratio must be A/Bn where n >1
    AB2 = 200/200 = 1
    AB3 = 200/300 = 0.666

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