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Exam 5: General Chemistry
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Question 221
Multiple Choice
The primary chemical composition of kidney stones commonly includes Ca
3
(PO
4
)
2
(calcium phosphate) , CaC
2
O
4
(calcium oxalate) , and MgNH
4
PO
4
(magnesium ammonium phosphate) . The metal ions in these compounds are:
Question 222
Multiple Choice
Passage Household cleaners commonly contain either ammonia (NH
3
) or bleach (NaOCl) as the principal active ingredient. Mixing ammonia-based and bleach-based cleaners can be hazardous, as the resulting reactions can form several toxic products. One of these reactions forms the irritant dichloramine (NHCl
2
) as follows:
Reaction 1
The overall reaction has a standard enthalpy change of −55 kJ/mol and a standard entropy change of −150 J/mol·K. Partial thermodynamic data for formation of Reaction 1 reagents from their elements are shown in Table 1.
Table 1
Partial Data for Enthalpies, Entropies, and Free Energies of Formation of Several Compounds at 25 °C
After it is formed, dichloramine readily enters the gas phase, where it may be inhaled. In the lungs, dichloramine reacts with water to produce hydrochloric acid and ammonia, as well as reactive oxygen species. In small doses, these products cause mild irritation, but inhalation of large amounts of chloramines can lead to pneumonitis (inflammation of the lungs) and may require medical intervention. Adapted from Trogolo D, Arey JS. Benchmark thermochemistry of chloramines, bromamines, and bromochloramines: halogen oxidants stabilized by electron correlation. Phys Chem Chem Phys. 2015;17(5) :3584-98. -If large amounts of ammonia and bleach were mixed, emergency responders could help stop the reaction by doing which of the following?
Question 223
Multiple Choice
Passage Cyanide (CN
−
) is a powerful, rapid toxin that binds to the cellular respiratory enzyme cytochrome c oxidase. The resulting enzyme-cyanide complex blocks the transfer of electrons to oxygen in the last step of the electron transport chain. This results in cytotoxic anoxia, causing asphyxiation at the cellular level.Exposure to cyanide can occur from dietary sources, medical treatments, industrial applications, smoke inhalation (structural fires) , and intentional use (suicide) . While dietary exposure from moderate consumption of naturally occurring plant compounds such as cyanogenic glycosides rarely results in acute adverse effects in humans, chronic effects have been observed from prolonged diets with significant levels of these compounds. In the developed world, risk of significant cyanide exposure is most likely to result from smoke inhalation during building fires or from industrial/occupational exposures.The impact of a given exposure depends on the amount (dose, duration) , the chemical composition of the cyanide compound (HCN, NaCN, KCN) , and the route of exposure (inhalation, absorption, ingestion) . The ionic salts (NaCN, KCN) and free acid (HCN) forms of cyanide each have different acid-base properties that interact differently under the physiological conditions associated with each route of exposure.To better understand the toxicity of different forms of cyanide, animal models have been studied for comparison to known human exposure case studies. Table 1 presents a summary of selected animal toxicity studies that examine exposure via ingestion. The table provides the lethal dose to 50% of the population (LD
50
) in milligrams of cyanide per kilogram of body weight (mg/kg) .
Table 1
Compilation of LD
50
Cyanide Values in Various Animal Species
Based on animal models, one treatment developed for cyanide poisoning involves assisting the rhodanese enzyme in metabolizing CN
−
to SCN
−
via an intravenous solution of NaNO
2
and Na
2
S
2
O
3
. The Na
2
S
2
O
3
assists in the formation of a reactive S-SH (persulfide) bond in the enzyme on cysteine-247 (Reaction 1) , which then reacts with the cyanide ion to form thiocyanate (Reaction 2) .
Adapted from: Hall AH, Isom GE, Rockwood GA. Toxicology of Cyanides and Cyanogens, Experimental, Applied and Clinical Aspects. John Wiley & Sons; 2015: 1-20; and Egekeze JO, Oehme FW. Cyanides and their toxicity: A literature review. Vet Q. 1980; 2(2) : 104-114. -The base dissociation constant K
b
for the hydrolysis of an alkali metal cyanide salt is given by the relation:
where [OH
-
],[HCN], and [CN
-
] are the molar concentrations of the relevant chemical species. What is the pH of an aqueous solution that is 0.001 M in KCN salt? (Note: K
a
≈ 1 × 10
−9
for HCN, and pH ≠ pK
a
in this solution.)
Question 224
Multiple Choice
Which of the following molecular structures has the most hydrophobic character?
Question 225
Multiple Choice
Passage Students were asked to bring items from home to serve as examples for different types of reactions. The instructor provided additional reactants, solvents, heat, or a catalyst to demonstrate reactions with the household items.The students brought aluminum foil, table salt, sugar, baking soda, vinegar, toilet bowl cleaner, hydrogen peroxide, and antacid tablets.Experiment 1Reactions were performed using the household items. The reaction conditions and student observations are recorded in Table 1.
Table 1
Reaction Conditions and Visual Observations
Experiment 2The reactions that were observed to produce gas bubbles in Experiment 1 were repeated, and samples of the gases produced were collected. Each gas sample was tested by holding a burning (glowing) wooden splint within the reaction vessel to determine if the reaction evolved O
2
, H
2
, or CO
2
. A glowing splint placed in O
2
will burn more brightly, one placed in H
2
will ignite the gas, and one placed in CO
2
will be extinguished. The results of the gas tests are recorded in Table 2.
Table 2
Glowing Splint Gas Test Observations
-Based on the information in the passage, what is the identity of the gas formed from the decomposition of H
2
O
2
?
Question 226
Multiple Choice
The compressibility of a real gas and an ideal gas at a temperature of 200 K is shown as a function of pressure in the graph below.
Compared to the volume of the ideal gas at 350 atm, the volume of an equimolar amount of the real gas under identical conditions is:
Question 227
Multiple Choice
Passage The radiopharmaceutical 2-deoxy-2-(
18
F) fluoro-D-glucose (abbreviated as
18
F-FDG) is a modified form of D-glucose in which the hydroxyl group on the 2-carbon of the molecule has been replaced with a positron-emitting
18
F radionuclide. Synthesis of
18
F-FDG is accomplished in several steps involving both nuclear and chemical reactions, as shown in Figure 1.
Figure 1
Synthetic scheme for 2-deoxy-2-(
18
F) fluoro-D-glucoseInitially, a target of
18
O-enriched water (
18
OH
2
) is bombarded by protons using a cyclotron to achieve a (p-n) nuclear reaction in which a proton hitting the
18
O nucleus is absorbed by the nucleus, causing the ejection of a neutron and forming an
18
F nucleus. Following separation of the resulting
18
F
−
anions from the residual
18
OH
2
via an ion exchange column,
18
F
−
is used in a nucleophilic substitution reaction with an acetylated mannose triflate substrate. Subsequent hydrolysis to remove the acetyl protecting groups yields
18
F-FDG.Because
18
F-FDG is an analog of D-glucose, it is readily taken into cells by the same metabolic processes as D-glucose. Once inside the cells, the positron emissions of the
18
F radionuclide can be detected by positron emission tomography (PET) scans to produce diagnostic medical images of objects such as tumors. Emissions from the
18
F radionuclide subsequently diminish over time via radioactive decay (Figure 2) .
Figure 2
Nuclear decay of the
18
F radionuclideBecause of limitations in the spatial resolution of PET scanners, when an object (such as a tumor) is smaller than 30 mm in diameter, the measured specific uptake value (SUV) of
18
F-FDG accumulated within the object is lower than the actual SUV. The recovery coefficient (the ratio of the measured SUV to the actual SUV) shows that the measured SUV decreases as the size of the object decreases below the 30-mm threshold (Figure 3) .
Figure 3
Recovery coefficient as a function of object size in a PET scan with a spatial resolution of 7 mm using ordered subsets expectation maximization (OSEM) image processing Adapted from: S. Yu. "Review of F-FDG Synthesis and Quality Control." Biomed Imaging Interv J. ©2006 Department of Biomedical Imaging, Faculty of Medicine, University of Malaysa; and P. E. Kinahan, et al., "Positron emission tomography-computed tomography standardized uptake values in clinical practice and assessing response to therapy." Semin Ultrasound CT MR. ©2010 Elsevier. -Suppose that the (p-n) nuclear reaction described in the passage was attempted but resulted in the
18
O nucleus absorbing a proton without ejecting a neutron. The resulting nucleus formed would be an isotope of:
Question 228
Multiple Choice
At the end of the actinium nuclear decay series, polonium-215 decays in an alternating sequence of alpha and beta decays. What are the nuclei produced in the nuclear decay sequence listed in order of formation from first to last?