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Chem 113 Exam 3
Chapters 14-18
64
Chemistry
Undergraduate 1
04/24/2010

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Term
arrhenius acid
Definition
produces H+ in aqueous solutions
Term
arrhenius base
Definition
produces OH- in aqueous solutions
Term
bronsted-lowry acid
Definition
H+ donor
Term
bronsted-lowry base
Definition
H+ acceptor
Term
KA
Definition
[image]
Term
strong acid
Definition

yields a WEAK conjugate base ionization equilibrium lies far to the RIGHT. HCl HBr HI HClO4 HNO3 H2SO4

large Ka value.

smaller pKa value

will have H+ bound to F, N, or O atoms that can be donated

Term
Weak acid
Definition
ionization equilibrium lies far to the LEFT
weaker the acid, the stronger its conjugate base
Term
strong bases
Definition

LiOH NaOH KOH RbOH CsOH Ca(OH)2 Sr(OH)2

Ba(OH)2

larger Kb

smaller pKb

will have N or O atoms that have lone pair electrons that can attract H+

Term
amphoteric
Definition
can behave as either an acid or base
Term
acidic and basic solutions
Definition

if [H+] > [OH-] = solution is acidic if [H+] < [OH-] = solution is basic if [H+] = [OH-] = solution is neutral

Kw=[OH-][H+]

Kw=1.0x10-14

Term
The pH scale
Definition

pH=-log[H+] or -log[H3O+]

pH decreases as [H+] increases 

pH<7 = acidic solution

pH>7 = basic solution

pH=7 = neutral solution 

Term
If a solution of HCl has a pH of 4.50, what is the [H3O+] of the solution? Is this solution acidic, basic or neutral?
Definition

pH=-log[H+]=4.5

log[H+]=-4.5

10log[H+]=10-4.5

[H+]=3.16x10-5 M

 

the solution is acidic 

Term
percent ionization
aka: percent dissociation
Definition

[H3O+]from HA

             ______________ x 100 %

[HA]initial

 

Term
Kw
Definition

Ka x Kb = Kw

 

pKa + pKb = pKw

Term
polyprotic acids
Definition
an acid that contains more than one ionizable H atom per molecule
Term
acid-base properties of salts (cations)
Definition

  • cations may act as acids in water except:

Li+Na+, K+, Rb+, Cs+, Ca2+, Sr2+, Ba+2

  • these are pH neutral
  • these are the conjugate acids of strong bases and are such super weak acids that they will not act as an acid in water 
  • (strong bases without OH-)

Term
acid-base properties of salts (anions)
Definition

 

  • anions may act as base in water except:

 

Cl-, Br-, I-, NO3-, HSO4-, ClO4-, BrO4-, IO4-

 

  • these are pH neutral
  • these are the conjugate bases of strong acids and are such super weak bases that they will not act as a base in water
  • (strong acids without H+)

 

Term
oxyacids
Definition

  • contains the group H-O-X
  • for a given series the acid strength increases with an increase in the number of oxygen atoms attached to the central atom
  • the greater the ability of X to draw electrons toward itself, the greater the acidity of the molecule

Term
lewis acid
Definition
electron PAIR acceptor
Term
lewis base
Definition
electron PAIR donor
Term
common ion effect
Definition

the suppression of the ionization of the ionization of a weak electrolyte caused by the addition of an ion that is also a product of the ionization equilibrium of the weak electrolyte

  • shift in equilibrium position that occurs because of the addition of an ion already involved in the equilibrium reaction.

Term
buffered solutions
Definition
resists a change in pH
they are weak acids containing a common ion
after addition of strong acid or base, deal with stoichiometry first, then the equilibrium
Term
Henderson-Hasselbalch Equation for Buffers
Definition
pH = pKa + log (nbase/nacid)
Term
characteristics of buffered solutions
Definition
buffers contain relatively large amounts of weak acid and corresponding conjugate base
added H+ reacts to completion with the conjugate base
added OH- reacts to completion with the weak acid
Term
buffering capacity
Definition

the amount of acid or base that a buffer can neutralize before its pH changes is appreciable

  • when the ratio nbase/nacid is close to 1, the buffer has its maximum buffer capacity 

Term
buffer region
Definition
a weak acid/conjugate base pair acts best as a buffer around the pH region equal to the pKa. usually within ± 1 pH unit of the pKa
Term
equivalence point
Definition
point in the titration when enough titrant has been added to react with the substance in solution being titrated
Term
solubility
Definition
how much of a substance that will dissolve in a given amount of solvent at a given temperature
Term
solubility product
Definition

the equilibrium constant expression for a salt dissolving in water

CaF2(s) ↔ Ca2+(aq) +2F-(aq)

Ksp= [Ca2+][F-]2

the larger the Ksp, the more solid that will dissolve

Term
precipitation and qualitative analysis
Definition

  • Q > Ksp ; precipitation occurs and will continue until the concentrations are reduced to the point that they satisfy Ksp
  • Q < Ksp ; no precipitation occurs

Term
complex ion
Definition
a charged species consisting of a metal ion surrounded by ligands
Term
ligands
Definition
a lewis base (a molecular ion having a lone electron pair that can be donated to an empty orbital on the metal ion to form a covalent bond)
Term
spontaneous process
Definition
a change that occurs in a system left to itself; once started no external action is necessary to make this process continue Ex: the "souring" of cream
Term
nonspontaneous process
Definition
will not occur unless some external action is continuously applied
Ex: riding on a playground swing
Term
thermodynamics
Definition
lets us predict whether a process will occur but gives no information about the amount of time required for the process
Term
entropy
Definition

thermodynamic property related to the degree of disorder in a system

 

tends to increase if:

 

  • liquids are formed from solids 
  • gases are formed from either solids or liquids
  • the number of molecules of gas increases as a result of a chemical reaction
  • the temperature of a substance increases 
  • the more complex the molecule

 

Term
entropy change ΔS
Definition

the difference in entropy between two states

 

  • nature tends toward disorder. ie: a driving force for a spontaneous process is an increase in the entropy of the universe

to determine the sign of ΔS°, look at the coefficients of the gases

 

Term
positional entropy
Definition

a gas expands into a vacuum because the expanded state has the highest positional probability of states available to the system

 

therefore;

Ssolid < Sliquid << Sgas

 

greater volume, the greater the entropy 

Term
the second law of thermodynamics 
Definition

in any spontaneous process there is always an increase in the entropy of the universe

ΔSuniv>0

where ΔSuniv = ΔSsys + ΔSsurr

Term
the effect of temperature on spontaneity
Definition

 

  • the sign of ΔSsurr depends on the direction of the heat flow
  • the magnitude of ΔSsurr depends on the temperature
  • ΔSsurr =qrev/T = ΔH/T

 

qrev: heat gained in a reversible process (joules)

 

T: temperature (Kelvin)

 

  • since the change to the system is the reverse of the change to the surroundings 
ΔSsurr=ΔHsurr/T = - ΔHsys/T

Term
free energy
Definition

 

  • ΔG = ΔH - TΔS (from the standpoint of the system)
  • a process (at constant T, P) is spontaneous in the direction in which free energy decreases 
  • a "-" ΔG means "+" ΔSuniv
  • test for spontaneity
    • ΔG < 0 (negative) = spontaneous
    • ΔG >0 (positive) = nonspontaneous
    • ΔG = 0 = equilibrium
  • chemical equilibrium occurs at the lowest value of energy available to the reaction system
    • ΔG° = RTln(K) = ΔH° - TΔS°

 

Term
the dependence of free energy on pressure 
Definition

ΔG = ΔG° + RT ln(Q)

  •  
    • R: gas law constant; 8.3145 J/k*mol
    • T: temperature (kelvin)
    • Q: reaction quotient (in partial pressures)
    • ΔG°: the free energy change at the standard state

Term
free energy and work
Definition

  • maximum possible useful work obtainable from a process at constant temperature and pressure is equal to the change in free energy 
    • Wmax = ΔG
  • first law: you can't win, you can only break even.
  • second law: you can't break even. 

Term
electrochemistry
Definition
the study of the interchange of chemical and electrical energy
Term
oxidation-reduction (redox) reaction
Definition
involves a transfer of electrons from the reducing agent (loss of electrons) to the oxidizing agent (gain of electrons)
Term
oxidation
Definition
loss of electrons
Term
reduction
Definition
gain of electrons
Term
reducing agent
Definition
electron donor
Term
oxidizing agent
Definition
electron acceptor 
Term
half reactions
Definition
the overall reaction is split into two half reactions, one involving oxidation and one reduction.
Term
balancing by half-reaction method in ACID
Definition

  • write separate reduction, oxidation reactions.
  • for each half reaction:
    • balance elements (except H,O).
    • balance O using H2O.
    • balance H using H+.
    • balance charge using electrons.
  • If necessary, multiply by integer to equalize electron count.
  • Add half reactions.
  • check that elements and charges are balanced.

Term
half-reaction method balancing in BASE
Definition

  • balance as in acid
  • add OH- that equals H+ions (both sides!)
  • form water by combining H+, OH-
  • check elements and charges for balance

Term
galvonic cells
Definition

a device in which chemical energy is changed into electrical energy.

this is done with a oxidation-reduction (redox) reaction.

when a half reaction is reversed, the sign of E° is reversed.

when a half-reaction is multiplied by an integer,E° remains the same. 

a galvanic cell runs spontaneously in the direction that gives a positive value for E°cell

Term
anode
Definition
the electrode where oxidation occurs
Term
cathode
Definition
the electrode where reduction occurs
Term
cell potential or electromotive force (emf)
Definition
the "pull" or driving force on the electrons (E°)
Term
volt
Definition
the unit of electrical potential defined as one joule of work per coulomb of charge transferred
Term
volt meter
Definition
an instrument that measures cell potential by drawing electrical current through a known resistance
Term
line notation
Definition

 

  • anode components are listed to the LEFT
  • cathode components are listed to the RIGHT
  • anode and cathode are separated by double vertical lines.
  • a phase difference is indicated by a single vertical line.
Mg (s) | Mg2+ (aq) || Al3+ (aq) | Al (s)

 

Term
maximum cell potential
Definition

directly related to the free energy difference between the reactants and the products in the cell

ΔG°= -nFE°

n=numbers of moles of electrons

F=Faraday = 96,485 coulombs per mole of electrons 

Term
the Nernst equation
Definition

used to calculate the potential of a cell in which some or all of the components are not in their standard states.

E = E° - (RT/nF)*(ln(Q))

at 25° C, the nernst equation becomes.....

E= E° - (0.0591/n)*(log(Q))

Term
ion-selective electrodes
Definition
an electrode sensitive to the concentration of a particular ion in solution
Term
glass electrode
Definition
an electrode for measuring pH from the potential difference that develops when it is dipped into an aqueous solution containing H+ ions.
Term
electrolysis
Definition
process that involves forcing a current through a cell to cause a nonspontaneous chemical reaction to occur.
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