9/29/2020 IP 3.

Protocol: Chemical Principles II Laboratory

IP 3. Protocol
Acids and Bases in Water: Reac ons and Equilibrium
Introduc on
Watch the conceptual introduction video (https://bit.ly/3gjaHce) for this experiment.

In this experiment, we will investigate acids and bases using the Brønsted-Lowry theory as a
theoretical foundation. According to this theory, acids and bases are identified by their abilities to
donate and accept protons, respectively. In aqueous solutions, acids HA donate protons to water,
forming the conjugate base A– and hydronium ion H3O+. The equilibrium constant associated with
this reaction is called the acid dissociation constant Ka.

HA(aq) + H2O(l) ⇄ A–(aq) + H3O+(aq)

Bases accept protons from water, forming the conjugate acid HB+ and hydroxide ion OH–. The
equilibrium constant associated with this process is called the base association constant Kb.

B(aq) + H2O(l) ⇄ HB+(aq) + OH–(aq)

Ka and Kb serve as quantitative measures of the strength of an acid or base, the extent to which it
reacts in the forward direction in the above equations. For conjugate pairs differing in the presence or
absence of a single proton, we can identify a special relationship between the strength of the acid
and the strength of the conjugate base. Namely, the stronger the acid, the weaker its conjugate base,
and vice versa. Mathematically, we recognize this idea in the inverse relationship between Ka(HA)
and Kb(A–). At or near 25 ºC,

KW = Ka(HA) × Kb(A–) = 10–14

Hence, given Ka for an acid we can calculate Kb for its conjugate base and given Kb for a base we
can calculate Ka for its conjugate acid.

In studying solutions of acids and bases, we are most often concerned with the concentrations of the
species involved in the reactions above. So far, we have measured concentration either by relying on
a given molarity of stock solution or using spectroscopy and the Beer-Lambert law. For example, in
Experiment 15, the absorbance of the product was used to determine its concentration in a mixture at
equilibrium. In an acid-base context, the concentration of hydronium ion can be measured directly
as pH, the negative base-10 logarithm of hydronium ion molarity. Because acid-base reactions are
rapid, measured pH values always reflect equilibrium concentrations of hydronium ion.

pH = –log10([H3O+]eq)

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The “p” operator can also be applied to Ka and Kb to generate “human-friendly” versions of these
constants: pKa and pKb. These are nothing but the negative value of the exponent when Ka or Kb is
written as a power of 10. Note however that because of the negative sign in the definition of “p,”
lower pKa and pKb values are associated with stronger acids and bases respectively.

pK = –log10(K)

We will make several measurements of pH throughout this experiment with the aim of assessing
acid/base strength and determining pKa and pKb values. Keep in mind that concentrations of
hydronium and hydroxide ions in aqueous solutions are related by the auto-ionization of water. Thus,
pOH can be calculated from pH and vice versa. At or near 25 ºC,

KW = [H3O+]eq[OH–]eq = 10–14

pH + pOH = 14

To measure pH, we will make use of a LabQuest pH probe. The probe works by measuring the
voltage difference across a thin membrane due to a difference in H3O+ concentration across the
membrane. The probe should be handled with extreme care, as the glass membrane is very fragile.
Furthermore, it’s important to give the probe some time to come to equilibrium with the solution of
interest; gently swirl the pH probe in the solution and allow it to sit for at least thirty seconds before
recording a measurement. If the pH measurement is changing over time, record an approximate
average value to two decimal places.

In the first part of this experiment, we will study the acid dissociation reaction of acetic acid (HOAc).

HOAc(aq) + H2O(l) ⇄ OAc–(aq) + H3O+(aq)

You will prepare a solution of acetic acid from a given stock solution and measure its pH at
equilibrium in order to determine its pKa.

pH provides a measure of the hydronium and hydroxide concentrations, but does not directly give us
a sense of how much of the initially added acid or base reacts to form hydronium or hydroxide. To get
a sense of this, we can calculate percent deprotonation and percent protonation. For an acid
dissociation process, percent deprotonation is simply the fraction of HA molecules initially present
that react with water to form A– and H3O+ at equilibrium, expressed as a percentage. Because the
equilibrium concentrations of conjugate base and hydronium ion are equal provided the
concentration of the acid is large (both come from reaction of the acid with water), we can write
percent deprotonation as the ratio of the equilibrium concentration of hydronium ion to
the initial concentration of acid.

Percent protonation is the analogous concept for base association reactions: it represents the
fraction of base molecules initially present that react with water to form HB+ and OH– at equilibrium,

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expressed as a percentage.

Note that we will use these terms in this experiment in lieu of percent dissociation and percent
association, which are more ambiguous. In the second part of this experiment, we will use
measurements of pH to identify an unknown acid and explore the relationship between concentration
and percent deprotonation of a weak acid.

So far, we have dealt primarily with neutral acids HA and neutral bases B. However, acids and bases
need not be neutral, and many important acids and bases are charged. Because charged particles
cannot exist without counterions in macroscopic materials, an acidic or basic ion is always
accompanied by a different ion of opposite charge in an ionic compound or salt. The key to
appreciating the ability of many salts to change the pH of water from neutral is to recognize how
individual ions can act as acids or bases.

To predict whether a particular salt will act as an acid or base in water, we separate it into its
constituent ions and evaluate the acidic or basic behavior of the ions individually. Anions without
hydrogens will act as bases, cations with hydrogens will act as acids, and anions with hydrogens
may act as acids or bases. We then identify the strongest ion (that is, the most reactive) using either
qualitative arguments or pKa/b values. We will refer to the most reactive ion as the active ion in a salt.

After identifying the active ion and determining whether it will act as an acid or a base, we can apply
concepts from chemical equilibrium to determine the theoretical pH of a salt solution. For active ions
that are strong acids or bases, the molarity of the ion (not necessarily equal to the molarity of the
salt!) gives the concentration of hydronium or hydroxide directly. For active ions that are weak acids
or bases, an ICE table can be used to determine equilibrium concentrations and pH. Counterions can
be completely ignored in this process, but it is important to take stoichiometry into account.

In the final part of this experiment, we will investigate the acidic or basic behavior of ionic salts in
aqueous solution. All of the salts are solids that dissolve readily in water. When preparing solutions of
these compounds, make sure to account for waters of hydration, which are included in the solid.
Waters of hydration do not impact the acidic or basic behavior of the salts.

Name Molecular Formula

ammonium chloride NH4Cl

pyridinium chloride (NC5H6)Cl

sodium acetate trihydrate NaC2H3O2·3H2O

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Name Molecular Formula

sodium dihydrogen phosphate

NaH2PO4·H2O
monohydrate

disodium hydrogen phosphate

Na2HPO4·7H2O
heptahydrate

sodium carbonate Na2CO3

Safety and Materials

Do not share manually recorded data with your lab partner physically in the lab. You MUST maintain
six feet of distance between yourself and others in the room as much as possible. Merge the data
you collected with the data your lab partner collected after the lab period via direct messages in
Teams.

Watch the video introduction to reagents, glassware, and instruments

(https://www.youtube.com/watch?v=rntXIDWVZJU) for this experiment.

When working with an acid or base, there are three important things to consider:

1. The intrinsic strength of the reagent

2. The concentration of the reagent
3. How the reagent is used in the experiment

The intrinsic strength of an acid or base is reflected in its pKa or pKb value. Generally, acids or bases
with pK less than zero in water are considered strong. Even at moderate concentrations (e.g., 0.5
M or below), these reagents can cause burns upon contact with skin. Strong acids and bases should
always be treated with care, no matter their concentrations. The risk associated with a solution of a
weak acid or base depends on its concentration. At high concentrations, these reagents contain high
concentrations of hydronium or hydroxide ions, making them just as hazardous as strong acids or
bases. Where exactly the cutoff lies between “high” and “low” concentrations depends on pK for the
acid or base.

Concentrated (undiluted) acids and bases should always be handled with the utmost care, even if the
reagent is weak in a pK sense. Concentrated acids may give off fumes of the acid (or derivative) in
gaseous form, presenting an inhalation risk. Avoid removing concentrated acids or bases from the
fume hood; instead, transfer them into their reaction vessel inside the hood.

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The following reagents will be available:

0.50 M acetic acid solution (https://www.lobachemie.com/lab-chemical-msds/MSDS-acetic-acid-

05m-05n-standardized-solution-traceable-to-R100C-EN.aspx)
pH 4 buffer solution
pH 7 buffer solution
0.10 M formic acid solution (https://us.vwr.com/store/asset?
assetURI=https://us.vwr.com/stibo/hi_res/eng_us/35/79/10253579.pdf)
0.10 M ascorbic acid solution (http://www.labchem.com/tools/msds/msds/LC11530.pdf)
0.10 M acetic acid solution (http://www.labchem.com/tools/msds/msds/LC10350.pdf)
Ammonium chloride (NH4Cl) solid
Pyridinium chloride (C5H5NCl) solid (https://www.fishersci.com/shop/msdsproxy?
storeId=10652&productName=AC222281000)
Sodium acetate trihydrate (NaO2C2H3⋅ 3H2O) solid (https://beta-
static.fishersci.com/content/dam/fishersci/en_US/documents/programs/education/regulatory-
documents/sds/chemicals/chemicals-s/S25531.pdf)
Sodium dihydrogen phosphate monohydrate (NaH2PO4⋅ 3H2O) solid
(https://www.fishersci.com/store/msds?
partNumber=S369500&productDescription=SOD+PHOSPHATE+MONO+CERT+500G&vendorId=VN00
033897&countryCode=US&language=en)
Disodium hydrogen phosphate heptahydrate (Na2HPO4⋅ 7H2O) solid
(https://www.fishersci.com/store/msds?
partNumber=S3733&productDescription=SOD+PHOSPHATE+DIBAS+CR+ACS+3KG&vendorId=VN00
033897&countryCode=US&language=en)
Sodium carbonate (Na2CO3) solid (https://beta-
static.fishersci.com/content/dam/fishersci/en_US/documents/programs/education/regulatory-
documents/sds/chemicals/chemicals-s/S25539D.pdf)

NOTE: It is imperative that you minimize prolonged close contact with your lab partner and
classmates during the experiment. Use movement directions and other posted guidelines, listen
carefully to your teaching assistant, and follow the procedure below carefully to ensure appropriate
distancing.

Relevant Experimental Techniques

Weighing Solids (https://gatech.instructure.com/courses/139484/pages/weighing-solids)
Pipetting Liquids (https://gatech.instructure.com/courses/139484/pages/pipetting-liquids)
Preparing Solutions (https://gatech.instructure.com/courses/139484/pages/preparing-solutions)
Measuring pH with a LabQuest 2
(https://gatech.instructure.com/courses/139484/pages/measuring-ph-with-a-labquest-2)

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Procedures
A. pH of Ace c Acid Solu ons and Measuring pKa

Partner I (Partner with the Earlier Birthday)

1. Prepare an aqueous solution of acetic acid with precise concentration. Your TA will assign you a
concentration of acetic acid from the following choices: 0.050 M, 0.10 M, 0.20 M, 0.30 M, 0.40 M,
and 0.45 M. Design and record in your lab notebook a procedure to prepare 100.0 mL of your
assigned solution from the stock 0.50 M acetic acid solution provided. Use good technique to
ensure that the concentration of your solution is accurate—our goal is to accurately measure the
pKa of acetic acid.
2. Measure the pH of the solution. Once your lab partner has finished setting up the LabQuest and
pH sensor, pour the solution into a 250 mL beaker and immerse the pH probe in the solution.
Allow the probe to equilibrate with the solution for at least 30 seconds, then record its pH.
Calculate the pKa of acetic acid based on your measurements. Add your initial concentration of
acid, measured pH, and calculated pKa to a table on the board in your lab. Make sure to record
the measurements of your entire section.
3. Discard any remaining acetic acid solution down the drain. Between measurements, store the pH
probe in a beaker of deionized water.

Partner II (Partner with the Later Birthday)

1. Set up the LabQuest and pH sensor, calibrating the sensor with buffer solutions of known pH.
Obtain a LabQuest 2 and pH sensor and connect the sensor to the LabQuest using Sensors →
Wireless Device Setup → Go Wireless.
2. The probe needs to be calibrated before it can be used to measure pH accurately. We will use
buffers with known pH values for this purpose. Obtain jars of pH 4 buffer solution and pH 7
buffer solution. Do not pour out the buffer solutions; use the jars directly. Select Sensors →
Calibrate on the LabQuest, unscrew the storage solution cap to loosen the probe, and pull it out
of the storage solution. Set the storage solution aside and out of your way to prevent spillage.
3. Use a beaker of deionized water to wash off the probe and gently pat it dry with a paper towel or
Kimwipe. Place the probe in the pH 4 buffer solution and allow it to equilibrate with the buffer for
30 seconds. At the end of this time, type in “4.00” as the known value and press Keep to store the
calibration point.
4. Wash off the probe in the beaker of deionized water, pat dry with a paper towel or Kimwipe, and
place the probe in the pH 7 buffer solution. Allow the probe to equilibrate with the buffer solution
and type in “7.00” as the known value. Press Keep to store the second calibration point and press
OK to finish the calibration. Move the probe to the beaker of deionized water for storage—the
probe should be kept wet throughout the experiment.

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5. Make sure to record your measured pH value and calculated pKa, as well as the concentrations
and values recorded by the rest of your section.

Concept Check, Part 1

Brønsted acids and bases dissolved in water reach equilibrium extremely quickly with respect to acid
dissociation. Consider how a system containing acid in water evolves spontaneously over time. In
your lab notebook, write a balanced chemical equation for the reaction that occurs when acetic acid
(HOAc, pKa = 4.74) is dissolved in water and write the equilibrium expression for this reaction. Then,
draw a graph of the reaction quotient Q as a function of time, imagining the initial state at t = 0 as one
in which none of the dissolved HOAc has reacted. Plot pQ (= –log10 Q) on the y-axis and time on the
x-axis as shown below.

Label the value to which pQ converges at long reaction times. Use your measurements to position
this value at the right place on the graph.

B. Iden fying an Unknown Acid; Percent Deprotona on and Dilu on

Partner I

1. Prepare diluted solution II and measure the pH of solution I. For this part of the experiment, your
TA will assign you one unknown weak acid from the following options: acetic acid, formic acid,
and ascorbic acid. Stock solution of your 0.100 M weak acid will be provided. Design a
procedure to prepare diluted solution II from the stock solution in the volume indicated (preparing
the solutions in test tubes is ideal). See the table below.
2. Measure and record the equilibrium pH value of solution I using a pre-calibrated pH probe.
Calculate the pKa of the acid based on your measurements and identify the acid (later) by
comparing to known pKa values.

Solution Concentration (mol/L) Volume (mL) Notes

I 0.100 (stock) 20.0 Just 20.0 mL of stock solution.

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Solution Concentration (mol/L) Volume (mL) Notes

II 0.0100 20.0 1:10 dilution of solution I.

III 0.00100 20.0 1:100 dilution of solution I or 1:10 dilution of solution

Partner II

1. Prepare diluted solution III and measure the pH values of solutions II and III. For this part of the
experiment, your TA will assign you one unknown weak acid from the following options: acetic
acid, formic acid, and ascorbic acid. Stock solution of your 0.100 M weak acid will be provided.
Design a procedure to prepare diluted solution III from the stock solution in the volume indicated
(preparing the solutions in test tubes is ideal). See the table below.
2. Measure and record the equilibrium pH value of solutions II and III using a pre-calibrated pH
probe. Calculate the pKa of the acid based on your measurements and identify the acid (later) by
comparing to known pKa values.
3. Discard any remaining acetic acid solution down the drain. Between measurements, store the pH
probe in a beaker of deionized water.

C. Acidic and Basic Salt Solu ons

Partner I

1. Prepare an aqueous solution of a salt with precise concentration. You will be provided with one of
six ionic solids (salts). Design a procedure to prepare 100.0 mL of a 0.100 M solution of your salt
in water. Use good technique to ensure that the concentration of your solution is accurate.
2. After your lab partner has measured the pH of the solution, be sure to record it. Make sure to
record the measurements of your entire section as well.

Partner II

1. Measure the pH of an aqueous salt solution. Measure the equilibrium pH of the salt solution
prepared by your lab partner. Calculate the pKa of the cation (for acidic salts) or the pKb of the
anion (for basic salts). Add your pH measurement and chemical equation to a table on the board
in your lab. Make sure to record the measurements of your entire section.
2. Discard your salt solution in the waste bottle in the lab. When your measurements are complete,
disconnect the pH probe from the LabQuest and place the probe back in the storage solution.
Disconnect the amplifier from the probe and return it to the charging station. Return the probe to
the holder for your lab room. Rinse all glassware you used for this experiment before returning it
to your drawers.

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Concept Check, Part 2

Consider the anion and cation in your salt. In your notebook, write a balanced chemical equation for
the reaction of the cation or anion with water (whichever is more reactive) based on your measured
pH and the structures of the cation and anion.

Post-lab Calcula ons and Data Workup

Complete the data workup spreadsheet
(https://gatech.instructure.com/courses/139484/files/15118057/download?wrap=1)
(https://gatech.instructure.com/courses/139484/files/15118057/download?wrap=1) and other
calculations using the instructions below.

Table 1. For each acetic acid solution, fill in the pH, the corresponding [H3O+] value, and the
calculated pKa value. Use Excel to calculate a mean and standard deviation for the pKa values.
Indicate the solution you prepared and measured with an “X” in the appropriate row.

Table 2. Fill in the pH values measured at 0.100, 0.0100, and 0.00100 M concentrations. Fill in the
percent deprotonation for each solution.

Table 3. Fill in the pKa of your unknown acid based on the 0.100 M solution, the unknown letter, and
the identity of the acid.

Figure 1. Prepare a graph of percent deprotonation versus initial acid concentration using the data in
Table 2. Include axes labels with units.

Table 4. For each salt solution, fill in the measured pH, the active ion (see the Introduction), and its
calculated pKa (for acidic salts) or pKb (for basic salts). Indicate the solution you prepared and
measured with an “X” in the appropriate row.

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