Nature of Acids and Bases
Acids and bases will neutralize one another to form liquid water and a salt.
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Describe the general properties of acids and bases, comparing the three ways to define them
Key TakeawaysKey PointsAn acid is a substance that donates protons (in the Brønsted-Lowry definition) or accepts a pair of valence electrons to form a bond (in the Lewis definition).A base is a substance that can accept protons or donate a pair of valence electrons to form a bond.Bases can be thought of as the chemical opposite of acids. A reaction between an acid and base is called a neutralization reaction.The strength of an acid refers to its ability or tendency to lose a proton; a strong acid is one that completely dissociates in water.Key Termsvalence electron: Any of the electrons in the outermost shell of an atom; capable of forming bonds with other atoms.Lewis base: Any compound that can donate a pair of electrons and form a coordinate covalent bond.Lewis acid: Any compound that can accept a pair of electrons and form a coordinate covalent bond.
Acids have long been recognized as a distinctive class of compounds whose aqueous solutions exhibit the following properties:A characteristic sour taste.Changes the color of litmus from blue to red.Reacts with certain metals to produce gaseous H2.Reacts with bases to form a salt and water.
Acidic solutions have a pH less than 7, with lower pH values corresponding to increasing acidity. Common examples of acids include acetic acid (in vinegar), sulfuric acid (used in car batteries), and tartaric acid (used in baking).
There are three common definitions for acids:Arrhenius acid: any substances that increases the concentration of hydronium ions (H3O+) in solution.Brønsted-Lowry acid: any substance that can act as a proton donor.Lewis acid: any substance that can accept a pair of electrons.
Acid Strength and Strong Acids
The strength of an acid refers to how readily an acid will lose or donate a proton, oftentimes in solution. A stronger acid more readily ionizes, or dissociates, in a solution than a weaker acid. The six common strong acids are:hydrochloric acid (HCl)hydrobromic acid (HBr)hydroiodic acid (HI)sulfuric acid (H2SO4; only the first proton is considered strongly acidic)nitric acid (HNO3)perchloric acid (HClO4)
Each of these acids ionize essentially 100% in solution. By definition, a strong acid is one that completely dissociates in water; in other words, one mole of the generic strong acid, HA, will yield one mole of H+, one mole of the conjugate base, A−, with none of the unprotonated acid HA remaining in solution. By contrast, however, a weak acid, being less willing to donate its proton, will only partially dissociate in solution. At equilibrium, both the acid and the conjugate base will be present, along with a significant amount of the undissociated species, HA.
Factors Affecting Acid Strength
Two key factors contribute to overall strength of an acid:polarity of the moleculestrength of the H-A bond
These two factors are actually related. The more polar the molecule, the more the electron density within the molecule will be drawn away from the proton. The greater the partial positive charge on the proton, the weaker the H-A bond will be, and the more readily the proton will dissociate in solution.
Acid strengths are also often discussed in terms of the stability of the conjugate base. Stronger acids have a larger Ka and a more negative pKa than weaker acids.
There are three common definitions of bases:Arrhenius base: any compound that donates an hydroxide ion (OH–) in solution.Brønsted-Lowry base: any compound capable of accepting a proton.Lewis base: any compound capable of donating an electron pair.
In water, basic solutions will have a pH between 7-14.
Base Strength and Strong Bases
A strong base is the converse of a strong acid; whereas an acid is considered strong if it can readily donate protons, a base is considered strong if it can readily deprotonate (i.e, remove an H+ ion) from other compounds. As with acids, we often talk of basic aqueous solutions in water, and the species being deprotonated is often water itself. The general reaction looks like:
Thus, deprotonated water yields hydroxide ions, which is no surprise. The concentration of hydroxide ions increases as pH increases.
Most alkali metal and some alkaline earth metal hydroxides are strong bases in solution. These include:sodium hydroxide (NaOH)potassium hydroxide (KOH)lithium hydroxide (LiOH)rubidium hydroxide (RbOH)cesium hydroxide (CsOH)calcium hydroxide (Ca(OH)2)barium hydroxide (Ba(OH)2)strontium hydroxide (Sr(OH)2)
The alkali metal hydroxides dissociate completely in solution. The alkaline earth metal hydroxides are less soluble but are still considered to be strong bases.
Acids and bases react with one another to yield water and a salt. For instance:
This reaction is called a neutralization reaction.
Key TakeawaysKey PointsAn Arrhenius acid increases the concentration of hydrogen (H+) ions in an aqueous solution, while an Arrhenius base increases the concentration of hydroxide (OH–) ions in an aqueous solution.The Arrhenius definitions of acidity and alkalinity are restricted to aqueous solutions and refer to the concentration of the solvent ions.The universal aqueous acid–base definition of the Arrhenius concept is described as the formation of a water molecule from a proton and hydroxide ion. Therefore, in Arrhenius acid–base reactions, the reaction between an acid and a base is a neutralization reaction.Key Termshydronium: The hydrated hydrogen ion ( $H_3O^+$ ).acidity: a measure of the overall concentration of hydrogen ions in solutionalkalinity: a measure of the overall concentration of hydroxide ions in solution
The Arrhenius Definition
An acid-base reaction is a chemical reaction that occurs between an acid and a base. Several concepts exist that provide alternative definitions for the reaction mechanisms involved and their application in solving related problems. Despite several differences in definitions, their importance as different methods of analysis becomes apparent when they are applied to acid-base reactions for gaseous or liquid species, or when acid or base character may be somewhat less apparent.
The Arrhenius definition of acid-base reactions, which was devised by Svante Arrhenius, is a development of the hydrogen theory of acids. It was used to provide a modern definition of acids and bases, and followed from Arrhenius’s work with Friedrich Wilhelm Ostwald in establishing the presence of ions in aqueous solution in 1884. This led to Arrhenius receiving the Nobel Prize in Chemistry in 1903.
As defined by Arrhenius:An Arrhenius acid is a substance that dissociates in water to form hydrogen ions (H+). In other words, an acid increases the concentration of H+ ions in an aqueous solution. This protonation of water yields the hydronium ion (H3O+); in modern times, H+ is used as a shorthand for H3O+ because it is now known that a bare proton (H+) does not exist as a free species in aqueous solution.An Arrhenius base is a substance that dissociates in water to form hydroxide (OH–) ions. In other words, a base increases the concentration of OH– ions in an aqueous solution.
Limitations of the Arrhenius Definition
The Arrhenius definitions of acidity and alkalinity are restricted to aqueous solutions and refer to the concentration of the solvated ions. Under this definition, pure H2SO4 or HCl dissolved in toluene are not acidic, despite the fact that both of these acids will donate a proton to toluene. In addition, under the Arrhenius definition, a solution of sodium amide (NaNH2) in liquid ammonia is not alkaline, despite the fact that the amide ion (
Arrhenius Acid-Base Reaction
An Arrhenius acid-base reaction is defined as the reaction of a proton and an hydroxide ion to form water:
Thus, an Arrhenius acid base reaction is simply a neutralization reaction.
Key TakeawaysKey PointsThe formation of conjugate acids and bases is central to the Brønsted-Lowry definition of acids and bases. The conjugate base is the ion or molecule remaining after the acid has lost its proton, and the conjugate acid is the species created when the base accepts the proton.Interestingly, water is amphoteric and can act as both an acid and a base. Therefore, it can can play all four roles: conjugate acid, conjugate base, acid, and base.A Brønsted-Lowry acid -base reaction can be defined as: acid + base
Originally, acids and bases were defined by Svante Arrhenius. His original definition stated that acids were compounds that increased the concentration of hydrogen ions (H+) in solution, whereas bases were compounds that increased the concentration of hydroxide ions (OH–) in solutions. Problems arise with this conceptualization because Arrhenius’s definition is limited to aqueous solutions, referring to the solvation of aqueous ions, and is therefore not inclusive of acids dissolved in organic solvents. To solve this problem, Johannes Nicolaus Brønsted and Thomas Martin Lowry, in 1923, both independently proposed an alternative definition of acids and bases. In this newer system, Brønsted-Lowry acids were defined as any molecule or ion that is capable of donating a hydrogen cation (proton, H+), whereas a Brønsted-Lowry base is a species with the ability to gain, or accept, a hydrogen cation. A wide range of compounds can be classified in the Brønsted-Lowry framework: mineral acids and derivatives such as sulfonates, carboxylic acids, amines, carbon acids, and many more.
Brønsted-Lowry Acid/Base Reaction
Keep in mind that acids and bases must always react in pairs. This is because if a compound is to behave as an acid, donating its proton, then there must necessarily be a base present to accept that proton. The general scheme for a Brønsted-Lowry acid/base reaction can be visualized in the form:
acid + base
Here, a conjugate base is the species that is left over after the Brønsted acid donates its proton. The conjugate acid is the species that is formed when the Brønsted base accepts a proton from the Brønsted acid. Therefore, according to the Brønsted-Lowry definition, an acid-base reaction is one in which a conjugate base and a conjugate acid are formed (note how this is different from the Arrhenius definition of an acid-base reaction, which is limited to the reaction of H+ with OH– to produce water). Lastly, note that the reaction can proceed in either the forward or the backward direction; in each case, the acid donates a proton to the base.
Consider the reaction between acetic acid and water:
Here, acetic acid acts as a Brønsted-Lowry acid, donating a proton to water, which acts as the Brønsted-Lowry base. The products include the acetate ion, which is the conjugate base formed in the reaction, as well as hydronium ion, which is the conjugate acid formed.
Note that water is amphoteric; depending on the circumstances, it can act as either an acid or a base, either donating or accepting a proton. For instance, in the presence of ammonia, water will donate a proton and act as a Brønsted-Lowry acid:
Here, ammonia is the Brønsted-Lowry base. The conjugate acid formed in the reaction is the ammonium ion, and the conjugate base formed is hydroxide.
Key TakeawaysKey PointsThe self- ionization of water can be expressed as:
Under standard conditions, water will self-ionize to a very small extent. The self-ionization of water refers to the reaction in which a water molecule donates one of its protons to a neighboring water molecule, either in pure water or in aqueous solution. The result is the formation of a hydroxide ion (OH–) and a hydronium ion (H3O+). The reaction can be written as follows:
This is an example of autoprotolysis (meaning “self-protonating”) and it exemplifies the amphoteric nature of water (ability to act as both an acid and a base ).
The Water Ionization Constant, KW
Note that the self-ionization of water is an equilibrium reaction:
Like all equilibrium reactions, this reaction has an equilibrium constant. Because this is a special equilibrium constant, specific to the self-ionization of water, it is denoted KW; it has a value of 1.0 x 10−14. If we write out the actual equilibrium expression for KW, we get the following:
However, because H+ and OH– are formed in a 1:1 molar ratio, we have:
Now, note the definition of pH and pOH:
If we plug in the above value into our equation for pH, we find that:
Here we have the reason why neutral water has a pH of 7.0; it represents the condition at which the concentrations of H+ and OH– are exactly equal in solution.
pH, pOH, and pKW
We have already established that the equilibrium constant KW can be expressed as:
If we take the negative logarithm of both sides of this equation, we get the following:
However, because we know that pKW = 14, we can establish the following relationship:
This relationship always holds true for any aqueous solution, regardless of its level of acidity or alkalinity. Utilizing this equation is a convenient way to quickly determine pOH from pH and vice versa, as well as to determine hydroxide concentration given hydrogen concentration, or vice versa.
Key TakeawaysKey PointsAn acid dissociation constant (Ka) is a quantitative measure of the strength of an acid in solution.The dissociation constant is usually written as a quotient of the equilibrium concentrations (in mol/L):
The acid dissociation constant (Ka) is a quantitative measure of the strength of an acid in solution. Ka is the equilibrium constant for the following dissociation reaction of an acid in aqueous solution:
In the above reaction, HA (the generic acid), A– (the conjugate base of the acid), and H+ (the hydrogen ion or proton) are said to be in equilibrium when their concentrations do not change over time. As with all equilibrium constants, the value of Ka is determined by the concentrations (in mol/L) of each aqueous species at equilibrium. The Ka expression is as follows:
Acid dissociation constants are most often associated with weak acids, or acids that do not completely dissociate in solution. This is because strong acids are presumed to ionize completely in solution and therefore their Ka values are exceedingly large.
Ka and pKa
Due to the many orders of magnitude spanned by Ka values, a logarithmic measure of the acid dissociation constant is more commonly used in practice. The logarithmic constant (pKa) is equal to -log10(Ka).
The larger the value of pKa, the smaller the extent of dissociation. A weak acid has a pKa value in the approximate range of -2 to 12 in water. Acids with a pKa value of less than about -2 are said to be strong acids. A strong acid is almost completely dissociated in aqueous solution; it is dissociated to the extent that the concentration of the undissociated acid becomes undetectable. pKa values for strong acids can be estimated by theoretical means or by extrapolating from measurements in non-aqueous solvents with a smaller dissociation constant, such as acetonitrile and dimethylsulfoxide.
Acetic acid dissociation: The acetic acid partially and reversibly dissociates into acetate and hydrogen ions.
Key TakeawaysKey PointsThe p-scale is a negative logarithmic scale. It allows numbers with very small units of magnitude (for instance, the concentration of H+ in solution ) to be converted into more convenient numbers, often within the the range of -2 – 14.The most common p-scales are the pH and pOH scales, which measure the concentration of hydrogen and hydroxide ions. According to the water ion product, pH+pOH =14 for all aqueous solutions.Because of the convenience of the p-scale, it is used to also denote the small dissociation constants of acids and bases, which are given by the notation pKa and pKb.Key Termsdissociation: the process by which compounds split into smaller constituent molecules, usually reversiblylogarithm: for a number $x$, the power to which a given base number must be raised in order to obtain x; written logbx.; for example, log216 = 4 because 24 = 16
pH and pOH
Recall the reaction for the autoionization of water:
This reaction has a special equilibrium constant denoted KW, and it can be written as follows:
Because H+ and OH- dissociate in a one-to-one molar ratio,
If we take the negative logarithm of each concentration, we get:
Here we have the reason that neutral water has a pH of 7.0 -; this is the pH at which the concentrations of H+ and OH– are exactly equal.
Lastly, we should take note of the following relationship:
This relationship will always apply to aqueous solutions. It is a quick and convenient way to find pH from pOH, hydrogen ion concentration from hydroxide ion concentration, and more.
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pKa and pKb
Generically, this p-notation can be used for other scales. In acid -base chemistry, the amount by which an acid or base dissociates to form H+ or OH– ions in solution is often given in terms of their dissociation constants (Ka or Kb). However, because these values are often very small for weak acids and weak bases, the p-scale is used to simplify these numbers and make them more convenient to work with. Quite often we will see the notation pKa or pKb, which refers to the negative logarithms of Ka or Kb, respectively.