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What is analytical chemistry focus on?
Separation, identification, & determination of the relative amounts of the components of natural and artificial materials.
What are three key classical chemistry methods?
> Volumetric.
> Gravimetric.
> Distillation.
Why are classical methods considered more accurate?
> Instruments can drift, add noise, and require calibration.
> Classical methods measure directly instead of relying on instrument calibration.
What are four key instrumental methods?
> Light-based spectroscopy.
> Mass spectrometry.
> Separation.
> Electrochemical.
What does qualitative analysis tell you?
What components in sample.
What does quantitative analysis tell you?
How much components in sample.
What are the general steps in chemical analysis?
> Make specific questions re. chemical measurement from general questions.
> Search chemical lit. for appropriate procedure / to devise one.
> Select rep material to analyze.
> Convert rep sample into form suitable for analysis.
> Confirm that method reliably produces results answering initial question.
> Measure the [analyte] in identical aliquots. Replicates and uncertainties are to be considered.
> Deliver complete report for intended audience.
> Conclusions may then point to starting over / reformulating question.
> How many # of decimal pts should the uncertainty have?
> How many units past certainty can you estimate?
> The same # of decimal pts as the magnitude.
> One unit past certainty.
What are the four general rules for identifying sig figs?
> All non-zero digits = significant.
> Zeroes appearing btwn non-zeroes = significant.
> Leading zeroes = not significant.
> Trailing zeroes after a decimal point = significant.
> Trailing zeroes w/o decimal point = not significant.
What is the exception to the general rules for sig figs regarding logarithmic measurements?
> # of sig figs in the original number = # of digits after decimal in the log.
> # of digits before decimal in the log = order of magnitude / power of 10.
What is the exception to the general rules for sig figs regarding exact meaurements?
Exact number will never limit the # of sig figs.
This is not super common b/c we always have a degree of uncertainty.
> After performing mathematical operations, how many sig figs can you have?
> When do you round after these operations?
> The least precise measurement sets the limit for how precise the final answer can be and how many sig figs there are.
> You only round your final answer, everything else is not rounded.
What’s the rule of sig figs when it comes to addition and subtraction without a common exponent?
Round off to the # of decimal places in the number w/ fewest decimal places.
What’s the rule of sig figs when it comes to addition and subtraction with a common exponent?
> Convert all to a common exponent.
> Add/sub normally.
> Round to the same # of decimal places as the least precise value.
What’s the rule of sig figs when it comes to multiplication & division?
Round off to the # of sig figs found in value containing lowest # of sig figs.
What condition is reached when no further changes occur in the amounts of reactants and products in a reversible reaction?
Equilibrium. Fwd & rev rxns cont but concentrations = constant.
What is the general equilibrium constant expression for aA + bB ⇌ cC + dD?
K = [C]ᶜ [D]ᵈ / [A]ᵃ [B]ᵇ
What happens if [Reactant] ↑ or [Product] ↑?
↑ Reactant → shift right (more products).
↑ Product → shift left (more reactants).
> How does equilibrium shift if pressure ↑?
> Why does equilibrium shift to the side with fewer moles of gas when pressure increases?
> Why does equilibrium shift to the side with more moles of gas when pressure decreases?
> Shifts to side w/ fewer mol of gas.
> Because fewer gas molecules = smaller V → lowers P, counteracting stress (Le Châtelier).
> Because more gas molecules = larger V → raises P, counteracting drop (Le Châtelier).
How does equilibrium shift if temperature ↑?
> Exothermic → shift left (heat = product).
> Endothermic → shift right (heat = reactant).
> What is Kw?
> How is Kw expressed?
> eq constant for H2O.
> Kw = [H3O+][OH-]
> What is ionic strength?
> What is the formula for ionic strength (\mu )?
A measure of the total concentration of ions in a solution.
u=\frac12\Sigma c_{}z^2_{}
Given the following situations, determine (1) what happens ionically & (2) in increase / decrease in ionic strength.
> Precipitation.
> Acid-base neutralization.
> Dilutions.
> Adding inert salt.
> Complex formation.
> Strong acid + strong base
> Precipitation → ions removed → decrease.
> Acid-base neutralization → new salt, new ions made → increase.
> Dilutions → all [ions] go down → decrease.
> Adding inert salt → more ions but no rxn → increase.
> Complex formation → ion binds another, fewer free ions, free ions drop → decrease.
> Strong acid + strong base → ions swapped, none lost → no change.
> What is effective concentration (activity)?
> What’s the formula for activity?
The “real” concentration that drives equilibrium, accounting for ion–ion interactions.
a=\gamma\left\lbrack X\right\rbrack
The coefficient is how we can apply ionic strength to eq.
Why is K more accurate when expressed with activities instead of concentrations?
> In ionic solutions, ions attract/repel → actual “free” conc ≠ measured conc
> So we use activity.
What’s the formula for the activity coefficient?
\log_{y}=\frac{-0.51Z^2\sqrt{I}}{1+\frac{a\sqrt{I}}{305}}
Just get antilog to find y = activity coeff.
What’s the difference between formality (F) and molarity (M)?
> Molarity (M) = [specific chemical species] as it actually exists in solution.
> Formality (F) = initial [species]tot, assuming it retains its chemical identity as a formula unit, even if it later dissociates or reacts.
> What’s the fraction of dissociation (α)?
> What does it tell you?
> What’s the formula for α?
> Ratio of molecules that dissociate compared to the initial number of molecules.
> How strong dissociation is.
a=\frac{\left\lbrack A^{-}\right\rbrack}{\left\lbrack A^{-}\right\rbrack+\left\lbrack HA\right\rbrack}=\frac{x}{x+\left(F-x\right)}=\frac{x}{F}
> What’s a buffer? What does it do?
> What does it contain?
> Buffer = chemical system resisting ∆pH by neutralizing added acid or added base.
> Buffer contains significant amounts of a weak acid and its conjugate base.
> What does the buffer’s weak acid neutralize?
> What does the buffer’s conjugate base neutralize?
> The weak acid neutralizes the added base, e.g. hydroxide ions.
> The conjugate base neutralizes the added acid, e.g. hydronium ions.
> What does a titration curve show you?
> What does the buffer zone in a titration curve show you?
> In a titration curve, at what pH will the buffer start to “buffer” or does it duty?
> In a titration curve, at what pH will the buffer stop “buffering” or give up?
> What does it mean when pH = pKa?
> Shows ∆pH of a solution as titrant (acid or base) is added.
> Has a buffer zone that shows you slow change in the pH due to the performance of the WA/CB.
> At pH = pKa - 1, it starts to buffer or resist pH.
> At pH = pKa + 1, it stops buffering and gives up resisting to pH changes.
> At pH = pKa, there is equal amount of [HA] and [A-], i.e. 50% weak acid and 50% conjugate base.
> If you add a strong acid to a buffer, will the buffer’s weak acid increase or decrease? Will the buffer’s conjugate base increase or decrease?
> If you add base to a buffer, will the buffer’s weak acid increase or decrease? Will the buffer’s conjugate base increase or decrease?
> If you add a strong acid to a buffer, you get more weak acid and less conjugate base.
> If you add a strong base to a buffer, you get less weak acid and more conjugate base.
What is the Henderson-Hasselbalch (HH) equation? What does it calculate for you?
This calculates the pH of the WA-CB pair of our buffer.
What are the three situations you will be placed in, in regard to the HH equation?
> All in one form, wherein the pH is MORE than one unit above the pKa or wherein the pH is LESS than one unit below the pKa.
> Both in equal amounts, wherein pH = pKa.
> pH is WITHIN one unit below or above the pKa and not equalling the pKa.