Chem Exam 2 Flashcards
Solution
Homogenous mixture that consists of one or more solutes uniformly dispersed at molecular or ionic level throughout a medium known as the solvent
- Not always liquid
Ex: Air: solution of nitrogen, oxygen, other gases
Former dental fillings: silver amalgams (mix of silver and mercury)
Homogenous mixture
Not possible to discern boundaries between components of the mixture. Ex: Normal saline (uniform throughout sample)
Phase Boundary
Separates regions of a mixture where the chemical or physical properties of the mixture change
Solute
Material that got dissolved; component kf solution present in smaller quantity. Ex: Sodium chloride
Solvent
Material that does dissolving, usually water
Molarity (molar concentration)
Moles of solute per liter of solution
M = mol of solute/L of solution (mol/L)
- Molar concentrations are conversion factors btw moles of material and liters of solution
- Depends on temperature of solution
Molar concentration will decrease at temperature increases
Molality (molal concentration)
Express concentration in terms of moles of solute per kilogram of solvent
m=mol of solute/kg of solute
- Used in physical chemistry -> quantities of solute and solvent are considered separately
- Mass is not temperature dependent, molality is not temperature dependent
- Less convenient in analysis bc quantities of a solution measured out by volume or mass in lab include both solute and solvent
- When doing stoichiometry, molality requires additional calculation to take into
Molarity vs Molality
Molality and molarity are never equal, but difference is is smaller as solutions become more dilute
Convert btw molarity and molality, need to know density of solution
molality of solution = x mol of solute/y kg of solvent
Percent by weight to volume
%w/v
The percent of concentration you encounter in a clinical setting when measuring out a volume of medicine in syringe
Grams of solute per 100mL of solution
%w/v = g of solute/100mL of solution
OR
%w/v= g of solute/mL of solution (100%)
First equation is useful as a conversion factor btw grams of solute and milliliters of solution
Second equation is useful tp calculate concentration of a solution
- To relate to percent by weight to percent weight to volume, use the density of solution
Percent by volume (%v/v): never used in analytical lab bc values are not additive
Equivalents (Eq)
Analogous to a mole
Normality
Analogous to molarity
Normality and equivalents
1 equivalent of a substance contains 1 mole of chemical reactivity
N= equivalents of solute/L of solution
Normality is equal to equivalents of solute per liter of solution
Unless context of chemistry is specified, normality is ambiguous
Parts per million
Concentration of extremely dilute solutions is sometimes expressed as part per million
A ppm concentration is analogous to a percent concentration, except you are comparing amount of solute to a million grams of solute instead of 100 gram.
ppm = g of solute/1x10^6g of solution =
g of solute/g of solution (1x10^6)ppm
Solubility
Some solutes are more soluble in given solute than others
The solubility of solute is amount of solute that will dissolve in a given amount of solvent at a given temp
Saturated solution contains maximum amount of a solute, as defined by its solubility. No more solute will dissolve in a solution saturated with solute. if solution is not saturated, more solute will dissolve in solution.
Supersaturated solution
Supersaturated solution contains more solute than allowed by solubility of solute.
- NOT a stable system, bc there is more solute dissolved in sample than solvent can accommodate
- Excess solute will come out of solution, crystallizing as a solid, separating as a liquid, or bubbling out as a gas
Ex: when blood or urine in kidneys become supersaturated with calcium oxalate or calcium phos, kidney stone can form - If solute is a gas in liquid solvent, will see bubbles forming in solution (Fizz when opening bottle of beer or soda)
Miscibility
Two liquids are miscible if they are soluble I each other in all proportions
Ex: Alcohol and water are miscible with each other.
Oil and water are immiscible
Like dissolves like
- Polar solutes are more soluble in polar solvents
- Nonpolar solutes are more soluble in non polar solvents; insoluble in water
- Most organic molecules are nonpolar
- Most ionic compounds are polar -> dissolve in water but not soluble in organic compounds (ether, hexane)
Energy Changes
When a solute dissolves in a solvent, there is an associated energy change and temperature change to solution
The energy change when using heat and cold packs is called heat of solution or the enthalpy of solution:
Δhsoln
Defined as the energy change that accompanies dissolving exactly 1 mole of solute in a given solvent
Enthalpy H is equal to the heat Q as long as the pressure remains constant
The energy change may be endothermic or exothermic
Whether the heat of solution is endothermic or exothermic depends on the relative magnitudes of the lattice energy and the heat of solvation
* If tearing the ions apart requires more energy than is released by solvation, then “Δ”Hsoln is going to be positive (endothermic)
- If the energy released by solvation is greater than the energy required to tear the ions apart, “Δ”Hsoln is going to be exothermic
Exothermic
- If the solution process is exothermic, energy flows out of the system (solvent and solute) into the surroundings, resulting in a temperature increase in the solution
- Energy is lost
Endothermic
- If the solution process is endothermic, energy flows from the surroundings into the system, resulting in a temperature decrease in the solution
- Energy is gained
Effect of Pressure on Solubility
As pressure increases, the solubility of a gaseous solute in a liquid solvent increases
* With less pressure, solubility of gaseous solute decreases (CO2 escaping champagne bottle)
- Since solids and liquids are not very compressible, at least not compared to gases, pressure has very little effect on the solubility of solid and liquid solutes
The quantitative relationship between pressure and solubility is given by Henry’s law:
S = k(H)P(gas)
S = solubility kH = Henry’s law constant (0.042g/L/atm Pgas = partial pressure of the gas
Increased partial pressure of gas -> more gaseous molecules zipping around at near surface of the liquid
Effect of Temperature on Solubility
The solubility of solid and liquid solutes in liquid solvents generally increases with increasing temperature
- As temperature increases, vapor pressure of gaseous solutes increases to point that they escape the solvent into gas phase
Colligative Properties
Vapor Pressure
The vapor pressure of a solution Decreases with increasing solute concentration
The vapor pressure of a liquid results from the most energetic molecules near the surface of the liquid escaping into the gas phase
The most likely escape sites for the liquid molecules are at or near the surface of the liquid
As we begin to introduce solute molecules, some of these escape sites are occupied by the solute molecules, so fewer solvent molecules can escape into the gas phase
Therefore, the vapor pressure of the solution is less than the vapor pressure of the pure solvent
Raoult’s law states the vapor pressure of a volatile component of a solution (P) is equal to the vapor pressure of the pure substance (Po) times the mole fraction (ᵡ) of that substance
P = χPo
Colligative Properties
Boiling Point
The boiling point of a solution INCREASES with increasing solute concentration
Temperature at which the vapor pressure of the material is equal to the ambient pressure
The boiling point of a solution increases as the concentration of solute(s) increases
The change in boiling point is directly proportional to the molal concentration of the solute particles
ΔTbp = Tbp,solution – Tbp,solvent = kbp · mtotal
ΔTbp = the number of degrees by which the boiling point increases Tbp,solution = the boiling point of the solution, Tbp,solvent = the boiling point of the pure solvent kbp = a constant (called the ebullioscopic constant) that is characteristic of the solvent mtotal = the molal concentration of all solute particles
Activity is the effective concentration of a solute
Activity is always less than molality
Colligative Properties
Freezing Point
The freezing point of a solution DECREASES with increasing solute concentration
Temperature at which the liquid phase of the material is in equilibrium with the solid phase
In order to enter into the solid state, the molecules (or ions or atoms) of the sample need to settle into an orderly, crystalline lattice structure
The presence of solute particles interferes with this process by getting in the way
It is necessary to cool the sample to lower temperatures, thereby lowering the kinetic energy of the molecules even further, before they will settle into the solid phase
The relationship that quantifies the degrees of freezing point depression has an identical form to boiling point elevation
ΔTfp = Tfp,solution − Tfp,solvent = kfp · mtotal
ΔTfp = the number of degrees by which the freezing point decreases Tfp,solution = the freezing point of the solution, Tfp,solvent = the freezing point of the pure solvent kfp = a constant (called the cryoscopic constant) that is characteristic of the solvent mtotal = the molal concentration of all solute particles
Colligative Properties
Osmotic Pressure
The osmotic pressure of a solution INCREASES with increasing solute concentration
Osmosis is diffusion of water through a semipermeable membrane
The relative concentration of solutes in osmotic systems is called the tonicity
Two solutions are isotonic if they contain equal concentrations of particles
Hypertonic: higher concentration of solute
Hypotonic: lower concentration of solute
Osmosis always spontaneously occurs from the hypotonic solution to the hypertonic solution
Diffusion always spontaneously occurs in the direction from an area of high concentration to an area of low concentration
Entropy demands that osmosis occur between two solutions of unequal tonicity until the concentrations of the two solutions are equal
Osmotic pressure (symbolized as capital pi, Π) results from the potential drive for the concentration of water to equalize
Osmotic pressure is a colligative property, and the osmotic pressure of a solution increases with increasing solute concentration
The relationship between osmotic pressure and concentration is given by:
ΠV = nRT
If the volume is in liters and we divide both sides of the relationship by volume, we get:
Π = MRT
where Π is the osmotic pressure, M is the molarity of the solute particles, R is the ideal gas constant, and T is the absolute temperature
Colloids
Similar to solutions in that they consist of one phase uniformly dispersed in a second phase
Examples: milk, blood, paint, and jelly
Not true solutions because the particles in the dispersed phase are not the size of molecules or ions
Particles in a colloid range in size from 10 nm to 200 nm
Colloidal particles cannot be filtered and do not settle out of solution
Colloids can be stable for years if they are stored under controlled conditions
Colloids exhibit the Tyndall effect, whereas solutions do not
Particles of a colloid are large enough to scatter light passing through
Particles in a true solution are too small to scatter visible light, so solutions do not exhibit the Tyndall effect
Chemical Equilibria
Le Châtelier’s Principle
States that equilibrium is a good thing, and nature strives to attain and/or maintain a state of equilibrium or homeostasis
Chemical Equilibria
Changing Concentration
If you add products, the equilibrium will shift toward reactants
If you remove products, the equilibrium will shift toward products
The system readjusts to counteract whatever change made
Chemical Equilibria
Changing Temperature
Increasing temperature favors endothermic processes
Chemical Equilibria
Changing Volume and Pressure
Significantly impacts equilibrium reactions only when at least one of the reactants or products is a gas bc liquids and solids are not compressible
Decreasing volume increases pressure -> smaller number of gas particles
The Equilibrium Constant
A system is in a state of equilibrium when there is a balance between reactants and products
This balance is defined by thermodynamic parameters, namely bond strengths and the intermolecular forces between all the molecules in the system
The equilibrium constant (K) is the numerical description of that balance
K is equal to the product of all of the molar concentrations of the products, each raised to the power of their stoichiometric coefficients, divided by the product of the molar concentrations of the reactants, each raised to the power of their stoichiometric coefficients
Subscripts
The equilibrium constant (K) is often appended with a subscript that denotes the type of equilibrium reaction
Keq is a generic equilibrium constant
Ka is an equilibrium constant governing the ionization of weak acids
Kb is an equilibrium constant governing the ionization of weak bases
Ksp is an equilibrium constant governing the solubility of sparingly soluble compounds
Meaning of K
As K increases, the reaction tends to increasingly favor products and the forward reaction becomes more favorable
As K decreases, the reaction tends to increasingly favor starting materials, and the reverse reaction becomes more favorable
Solids and Liquids
Pure solids or liquids comprise a different phase from where reactions in aqueous media occur
The concentration of pure solids and liquids is a constant value (or very nearly so), and these constant values for concentration are included with the equilibrium constant value
The concentration of solids, liquids, and water (as a solvent) do not appear explicitly in the equilibrium constant expression
Reversing a Reaction
When you reverse the equation for a chemical reaction, Kforward is the reciprocal of Kreverse
Kforward = 1/Kreverse
Definition of Acids and Bases
Arrhenius definition (most operational definition)
Acid–species that increases the hydronium ion (H3O+) concentration in an aqueous solution
Base–species that increases the hydroxide ion (OH–) concentration in an aqueous solution
Brønsted2 definition (most generally useful definition)
Acid–species that donates a hydrogen ion (H+) to a base
Base–species that accepts a hydrogen ion (H+) from an acid
Conjugate Acid-Base Pairs
The charge on the conjugate acid is always one greater than the charge on its conjugate base
When an acid gives away its hydrogen ion to a base, the acid is converted into its conjugate base
When a base accepts a proton from an acid, the base is converted into its conjugate acid
In generic form, we can express this process as:
HA + B → A− + BH+
Conjugate Base Ex: HNO3 -> NO3- (conjugate base)
Conjugate Acid Ex: H2O -> H3O+ (conjugate acid)
Amphiprotic Species
Can behave as either an acid or a base
Ex: H2O
Base w/ HCl -> H3O+ (becomes conjugate acid)
Acid w/ HCO3- -> OH- (becomes conjugate base)
Strong Acids
Acids donate protons
Very determined to foist their proton off onto a base
Essentially 100% ionized when dissolved in water, but this is not an equilibrating process, so all of the starting materials are converted into products
Strong acids are relatively rare, most acids are weak and only partially ionize in water
Ex: HCl, H2SO4, HI, HBr, HNO3
Strong Bases
Bases accept hydrogen ions
In water, the strongest possible base is the hydroxide ion, OH−
A strong base ionizes essentially 100% to produce the OH − ion, so a strong base is a soluble ionic hydroxide
Ex: LIOH, NAOH, KOH, Ba(OH)2
Weak Acids
Are able to donate hydrogen ions to bases, but are less determined to do so than strong acids
When a weak acid dissolves in water, it establishes a dynamic equilibrium between the molecular form of the acid and the ionized form
Ex: HC2H3O2, H2CO3, H3PO4, NH4+
Weak Bases
Are able to accept hydrogen ions from acids, but are less determined to do so than strong bases
Do not completely ionize in water to produce an equivalent concentration of the hydroxide ion, because when a weak base dissolves in water, it establishes a dynamic equilibrium between the molecular form and the ionized form
Ex: NH3, HCO3-, CO3^2-, HPO4^2
Polyprotic Acids
A diprotic acid has two hydrogen ions to donate, so a diprotic acid can behave as an acid twice
A triprotic acid has three hydrogen ions to donate
The number of acidic protons is not necessarily the number of hydrogens in the molecular formula
The reason for the dichotomy of hydrogen lies in the molecular structure of acetic acid
The acidic hydrogen is bonded to a highly electronegative oxygen atom
The O—H bond is polarized toward the oxygen to a point that a base can snatch away the hydrogen as an H+ ion from the acetic acid molecule
The other three hydrogens are bonded to a carbon atom, and carbon and hydrogen have almost identical electronegativities, so those bonds are nearly nonpolar and the hydrogens have no tendencies to be removed as H+ ions
Acid and Base Strength: Ka and Kb
Some acids are stronger than others
A stronger acid is more determined to give its proton to some base
A stronger base is more determined to take a proton from some acid
When a strong acid dissolves in water, it dissociates completely
All other acids are weak acids
The relative strength of a weak acid is quantified by the equilibrium constant Ka governing the ionization of the weak acid
A larger value of Ka means a stronger acid
Acid/Base Strength of Conjugate Acid–Base Pairs
The stronger the acid, the weaker its conjugate base
The stronger the base, the weaker its conjugate acid
General guidelines
The conjugate base of a really strong acid has no base strength
Ex: HCl is a strong acid; Cl- phase no base strength
The conjugate base of a weak acid has base strength
Ex: Acetic acid is a weak acid; acetate acid has base strength
The conjugate acid of a weak base has acid strength
Ex: Ammonia is a weak base; ammonium ion behaves like an acid in water
Acid-base reactions
Involve a transfer of a hydrogen ion from the acid to the base
In order to predict the products of an acid–base reaction:
Identify which is the acid and which is the base
Move an H+ ion from the acid to the base, converting the acid into its conjugate base and the base into its conjugate acid
Any acid–base reaction has two acids and two bases:
One acid and one base on the reactant side
Conjugate acid and conjugate base on the product side
The base almost always has a lower (more negative) charge than the acid
Also, hydrogen is almost always the first atom listed in the formula of an acid
The reaction equilibrium always favors the formation of the weaker acid
Look up the Ka’s for the reacting acid and the conjugate acid of the reacting base
Measuring acidity
The p-Function
The p in pH is a mathematical operator that means the negative logarithm of, and the H in pH means hydrogen ion concentration, so the definition of pH is:
pH = −log[H+]
p-function operator used to express the concentrations of many ions, but the meaning of the p is the same in every case—take the logarithm of the concentration and then change the algebraic sign
A logarithm function is a way to map a vast range of values onto a much smaller set of values
To apply the p-function, take the logarithm of the [H+] concentration and then change the sign
The value of the pH will be the same as the absolute value of the exponent when the first part of the scientific notation is exactly 1
pH values have no intrinsic units—logarithms represent “pure numbers”
Each change of 1 pH unit means the hydrogen ion concentration is changing by a factor of 10, so small changes in pH correspond to much larger changes in acidity level
Removing the p-function is accomplished by changing the sign of pH and then taking the antilog
Self-Ionization of Water
Water has some very weak acid–base properties, and therefore sets some limits on the parameters of the pH scale
A tiny fraction of water molecules dissociates or ionizes into a hydrogen ion and a hydroxide ion
H2O ⇄ H+ + OH−
The equilibrium constant that governs this equilibrium is called Kw
At 25°C, Kw = 1.0 × 10−14 so pKw is 14.00
Since water is a pure liquid, the concentration of water does not appear in the equilibrium constant
Kw = [H+] [OH−] = 1.0 × 10 −14 at 25°C
In pure water, the concentrations of the H+ and OH− ions are equal
[H+] = [OH−] in pure water
The pH of pure water is 7.00 because that is the negative logarithm of the hydrogen ion concentration that is generated by the self-ionization of water
Relationship Between pH and pOH
Because pH and pOH are derived from the ionization of water, there is a fixed relationship between them
The pH plus the pOH of any aqueous solution (at 25°C) always adds up to 14.00:
14.00 = pH + pOH
pKa and pKb
The equilibriums constants for acids and bases are commonly presented as p-functions
The pKa and pKb of a conjugate acid–base pair sum to give 14.00:
pKa + pKb = 14.00