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Buffer Cal:

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1st Law of T. 1st Entropy

(E-change internal energy of (Q-heat-energy transferred; T- temp. at Entropy is a state function,

Strong acids & bases dissociate completely n water. At the end of dissolution there r no molecules present only ions. Weak acids & bases dissociate partially n water. At the end, large # of molecules r present, w/ very few ions. Both establish equilibrium. If acetate ion is added 2 the soltn the equil shift 2 the left The extent of ionization of a weak electrolyte is decreased by addng 2 the solution a strong electrolyte that has an ion n common w/ the weak electrolyte. Buffers r solutions of a weak conjugate acid-base pair. partially resistant 2 drastic pH changes, even when strong acid/base is added. base & acid neutralize each other. The pH range-the range of pH values over which a buffer system works effectively. Its most effective 2 choose an acid w/ a pKa close 2 the pH desired. When strong acids or bases r added 2 a buffer all of the strong acid or base is consumed n the reaction. Titration-technique n which a known concentration of base/acid is slowly added 2 a solution of acid/base A pH meter or ndica2rs r used 2 determine when the solution has reached the equivalence point at which the s2ichiometric amount of acid equals that of base. Addition of strong acid or base 2 a buffer. 1. Determine how the neutralization reaction affects the # of the weak acid & its conjugate base n solution 2) Use the HendersonHasselbalch eqtn 2 determine the new pH of the solution. Titration of a strong acid w/ strong base: Just before/after the equivalence point (50ml of NaOH), the pH inc. rapidly. At the equivalence point, moles acid = moles base, & the solution contains only water & the salt from the cation of the base & the anion of the acid. As more base is added, the inc. n pH again levels off. Summary Strong Acid vs. Strong Base: 1) pH due 2 strong acid H+ 2) all OH- added is being consumed by equal amount of H+ 2 form H2O pH due 2 unreacted H+ 3) at equiv. pt, all H+ is used up 2 react w/ added OH- 2 form H2O pH due 2 NaCl & H2O 4) any OH- added isnt consumed by H+ bc it ran out pH due 2 unreacted OHthe conjugate base of the acid affects the pH when it is formed. At the equivalence pt the pH is >7. Phenolphthalen is commonly used as an ndica2r n these titrations. Weak acid vs. Strong Base: 1) Weak acid + its conjugate base= Buffer solution 2) Buffer solution resists change n pH 2a) pH due 2 weak acid HF 2b) all OH- added is beng used by equal amount of HF, HF +OH- yields F- +H2O, a buffer is system is established HF & F-; HF<>F- +H+; pH due 2 unreacted HF & H+ from the buffer 2c) At the equivalent pt, all HF has been used up 2 react w/ added OH- 2 form F- + H2O; pH due 2 F- & H2O 2d) Any OHadded is not consumed by HF bc it has run out; pH due 2 unreacted OH-

Henderson-Hasselbalch Eqtn:
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a system; q-heat absorbed; w- work) which energy is beng transferred) dependng only on nitial & fnal states 2nd Law of T. Reversible: Irreversible: 2nd Entropy The change n entropy: E. ncrease w/ the # of microstates n the system; snap shots = more E. Entropy changes for a reaction can be estimated n a manner analogous 2 that by which H is estimated ( ( ) ) where m & n r the coefficients n the (k is the Boltzmann constant,

Solubility Product: +

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] from From the start of the titration 2 near equivalence point, the pH slowly goes up

At each point the pH of the solution during titration is determined from the amounts of acid & its conjugate base present at that particular time.

balanced chemical eqtn Complex Ions: Metal ions can act as Lewis acids & form complex ions w/ Lewis bases n the solvent.

W/ weaker acids, the initial pH is higher & pH changes near the equivalence pt r more subtle.

The pH at the equivalence pt n these titrations is <7. Methyl red is the ndica2r of choice

When 1 titrates a Polyprotic acid w/ a base there is an equivalence pt for each dissociation

Ksp is not the same as solubility. Solubility is the mass of solute 1 L (g/L) or 100 mL (g/mL) of solution or mol/L (M)

A saturated solution is the 1 n which the dissolved solute is n equilibrium w/ the undissolved solute The Common Ion Effect: if you add 1 of the ions n a solution equil. that is already dissolved n the solution, the equil. will shift 2 the left & the solubility of the salt will dec. pH: if a substance has a basic anion, it will be more soluble n an acidic solution. Substances w/ acidic cations r more soluble n basic solutions. The formation of complex ions inc. the solubility of salts. Amphoterism: Amphoteric metal oxides & hydroxides r soluble n strong acid or base, bc they can act either as acids or bases. Ex. Al3+, Zn2+, & Sn2+. Will a Precipitate form? N a solution: if Q=Ksp, the system is at equilibrium & the solution is saturated. Ion concentrations r equal 2 concentration required at equilibrium. If Q<Ksp, more solid can dissolve until Q=Ksp. NO PPT. Ion concentrations r less than concentration required at equilibrium. Equilibrium shifts 2 the right 2 produce more ions until ion concentration reaches equilibrium. If Q>Ksp, the salt will precipitate until Q=Ksp. PPT. Ion concentrations r more than concentration required at equilibrium. Equilibrium shifts 2 the left, 2 use up ions until ion concentration reaches equilibrium. 1 can use differences n solubilities of salts 2 separate ions n a mixture Q<Ksp reaction goes Q=Ksp Equilibrium: Q>Ksp Reaction goes Heat that flows into or out of the system changes the entropy of the surroundings. Chem. Therm: chemical thermo. is concerned w/ energy relationships in chemical reactions- enthalpy & entropy. 1st Law of Thermo.: Energy cannot be created nor destroyed. The 2tal energy of the universe is a constant. Energy can be converted from 1 4m 2 another or transferred from a system 2 the surroundings or vice versa. Spontaneous Processes: Spontaneous processes r those that can proceed w/out any outside intervention. The gas in vessel B will spontaneously effuse in2 vessel A, but once the gas is in both vessels, it will not spontaneously return 2 vessel B. Spontaneous in 1 direction. Dropping an egg break it, picking it up does not un-break it. Processes that r spontaneous in 1 direction ate nonspontaneous in the reverse direction. Spontaneity is directional, the direction of the reaction affect whether the reaction is spontaneous or not. Spontaneous Processes: Experimental conditions such as temperature or pressure determines whether a process is spontaneous or not. Processes that r spontaneous at 1 temp r nonspontaneous at other temp. Spontaneous Processes: Above 0C (heating) it is spontaneous 4 ice (solid) 2 melt & 4m water (liquid). At above 0C (heating) it is not spontaneous 4 water 2

become ice. If you change temp below 0C (cooling) the reverse process becomes spontaneous. Consider a system & surrounding at the same temp. Heat flows between a system & its surroundings reversibly if the change in heat is infinitesimal (very small). The change in direction of heat flow is achieved by increasing or decreasing the temp of the system. If the surrounding remains constant, decreasing the temp causes heat 2 flow in the system. If surrounding remains constant, increasing the temperature causes heat 2 flow out of the system. Reversible Processes: In a reversible process the system changes in such a way that the system & surrounding can be put back in their original states by exactly reversing the process. Heat flows from a hotter object 2 a colder object. Irreversible Processes: Gas is confined 2 right half of the cylinder by partition. Partition is slid out 2 allow spontaneous change (spreading out of gas), no work is d1. Returning partition 2 its original position does not confine the same amount of gas 2 the right half of the cylinder. 2 confine the same amount of gas 2 the right half we must do work by compressing the pis2n. Irreversible processes cannot be und1 by exactly reversing the change 2 the system. Spontaneous processes r irreversible. Entropy: by Rudolph Clausius in the 19th century. Clausius was convinced of the significance of the ration of heat delivered & the temp at which it is delivered. It can be thought of as a measure of the randomness of a system. Its related 2 the various modes of motion in molecules. Like 2tal energy, E, & enthalpy, H, entropy is a state function. State function depends on the initial/final states. 4 a process occurring at constant temperature (an isothermal process), the change in entropy is equal 2 the heat that would be transferred if the process were reversible divided by the temp. 2nd Law of Thermo.: The second law of thermo. states that the entropy of the universe eqtns 4 spontaneous processes & the entropy of the universe does not change 4 reversible processes. Examine Statement: The second law of thermo. states that the entropy of the universe eqtns 4 spontaneous/irreversible processes. The entropy of the universe does not change 4 reversible processes. Ludwig Boltzmann described the concept of entropy on the molecular level. Temperature is a measure of the avg kinetic energy of the molecules in a sample. When a substance is heated, the motion of molecules eqtn. Higher temp results in molecules moving faster. Molecules have diff types of motion. Molecules exhibit several types of motion: Translationalmovement of the entire molecule from 1 place 2 another. Vibrational- Periodic motion of a2ms w/in a molecule.

Rotational: Rotation of the molecule on about an axis or rotation about o bonds. Boltzmann envisioned the motions of sample molecules at a particular instant He refused 2 this sampling(snap shot) as a microstate of the thermodynamic system. Each thermodynamic state (higher entropy, lower energy) has a specific # of microstates, W, associated with it Entropy of the molecular Scale: The # of microstates &, there4, the entropy tends 2 eqtn w/ eqtns in. Temp: More temp, more motion. Volume: More possible positions a molecule can occupy The # of indep. moving molecules. More molecules, more possibilities of diff microstates. Entropy Physical States: Entropy eqtns w/ the freedom of motion of molecules. There4e, S(g)>S(l)>S(s). Intermolecular 4ces restricts H20 from vibration motion only strong intermolecular 4ces, decrease entropy Solid has the strongest intermolecular 4ces, there4e less entropy. Solutions: A solid is dissolved in a solvent, entropy eqtns. Entropy eqtns when: Gases r 4med from liquids & solids. Liquids or solutions r 4med from solids. The # of gas molecules eqtns. The # of moles eqtns. Third Law of thermo.: the entropy of a pure crystalline substance at absolute zero is 0. Standard Entropies: Molar entropy values of substances in their st&ard states. St&ard entropies tend 2 eqtn w/ increasing molar mass. Larger & more complex molecules have greater entropies. Gibbs Free Energy: Gibbs free energy is a quantity that measures useful work from a system at constant temperature & pressure. Delta G gives us the theoretical maximum amount of useful work that can be d1 by a system on its surrounding. The energy if free 2 do useful work. The other energy is given off as heat. Gibbs Free Energy: 1) If delta G is neg., the 4ward reaction is spontaneous. 2) if delta G is 0, the system is at equil.. 3) If delta G is +, the reaction is spontaneous in the reverse direction.