Kinetic study of the dissociation of sodium cryptate(2,2,1)

Koji Ishihara, Hiroko Miura, Shigenobu Funahashi, Motoharu Tanaka

Research output: Contribution to journalArticle

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Abstract

The rate of dissociation of sodium cryptate(2,2,1) (NaCry+) has been measured at various temperatures and pressures in dimethyl sulfoxide (Me2SO), N,N-dimethylformamide (DMF), and acetonitrile (MeCN) by using a high-pressure stopped-flow apparatus with conductometric detection. There are two reaction paths: an acid-independent path (kd1), CryNa+ → Cry + Na+, and an acid-dependent path (kd2), CryNa+ + Hdca → CryH+ + Na+ + dca-, where Hdca is dichloroacetic acid. Activation parameters are as follows: in Me2SO, kd1/s-1 = (7.65 ± 0.05) × 10-1 (25°C), ΔVd1 /cm3 mol-1 = 2.1 ± 0.7, ΔHd1 /kJ mol-1 = 70.4 ± 0.8, and ΔSd1 /J mol-1 K-1 = -11 ± 3; in DMF, kd1/s-1 = (3.37 ± 0.03) × 10-1 (25°C), kd2/mol-1 kg s-1 (25°C), ΔVd1 /cm3 mol-1 = 2.0 ± 0.2, ΔVd2 /cm3 mol-1 = -8.8 ± 1.0, ΔHd1 /kJ mol-1 = 73.0 ± 0.9, ΔHd2 /kJ mol-1 = 30 ± 5, ΔSd1 /J mol-1 K-1 = -9 ± 3, and ΔSd2 /J mol-1 K-1 = -140 ± 20; in MeCN, kd2/mol-1 kg s-1 = 73.5 ± 0.5, ΔVd2 /cm3 mol-1 = -16.0 ± 0.8, ΔHd2 /kJ mol-1 = 41.1 ± 1.3, and ΔSd2 /J mol-1 K-1 = -71 ± 4. The reaction volume for the formation of NaCry+ in Me2SO has also been measured dilatometrically: ΔV° = 3.3 ± 0.4 cm3 mol-1. The reaction mechanism is discussed on the basis of these parameters.

Original languageEnglish
Pages (from-to)1706-1710
Number of pages5
JournalInorganic Chemistry
Volume27
Issue number10
Publication statusPublished - 1988
Externally publishedYes

Fingerprint

Dimethylformamide
Dichloroacetic Acid
Sodium
sodium
dissociation
acids
Kinetics
Acids
kinetics
Dimethyl Sulfoxide
Chemical activation
acetonitrile
activation
Temperature
temperature

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Ishihara, K., Miura, H., Funahashi, S., & Tanaka, M. (1988). Kinetic study of the dissociation of sodium cryptate(2,2,1). Inorganic Chemistry, 27(10), 1706-1710.

Kinetic study of the dissociation of sodium cryptate(2,2,1). / Ishihara, Koji; Miura, Hiroko; Funahashi, Shigenobu; Tanaka, Motoharu.

In: Inorganic Chemistry, Vol. 27, No. 10, 1988, p. 1706-1710.

Research output: Contribution to journalArticle

Ishihara, K, Miura, H, Funahashi, S & Tanaka, M 1988, 'Kinetic study of the dissociation of sodium cryptate(2,2,1)', Inorganic Chemistry, vol. 27, no. 10, pp. 1706-1710.
Ishihara K, Miura H, Funahashi S, Tanaka M. Kinetic study of the dissociation of sodium cryptate(2,2,1). Inorganic Chemistry. 1988;27(10):1706-1710.
Ishihara, Koji ; Miura, Hiroko ; Funahashi, Shigenobu ; Tanaka, Motoharu. / Kinetic study of the dissociation of sodium cryptate(2,2,1). In: Inorganic Chemistry. 1988 ; Vol. 27, No. 10. pp. 1706-1710.
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title = "Kinetic study of the dissociation of sodium cryptate(2,2,1)",
abstract = "The rate of dissociation of sodium cryptate(2,2,1) (NaCry+) has been measured at various temperatures and pressures in dimethyl sulfoxide (Me2SO), N,N-dimethylformamide (DMF), and acetonitrile (MeCN) by using a high-pressure stopped-flow apparatus with conductometric detection. There are two reaction paths: an acid-independent path (kd1), CryNa+ → Cry + Na+, and an acid-dependent path (kd2), CryNa+ + Hdca → CryH+ + Na+ + dca-, where Hdca is dichloroacetic acid. Activation parameters are as follows: in Me2SO, kd1/s-1 = (7.65 ± 0.05) × 10-1 (25°C), ΔVd1 ‡/cm3 mol-1 = 2.1 ± 0.7, ΔHd1 ‡/kJ mol-1 = 70.4 ± 0.8, and ΔSd1 ‡/J mol-1 K-1 = -11 ± 3; in DMF, kd1/s-1 = (3.37 ± 0.03) × 10-1 (25°C), kd2/mol-1 kg s-1 (25°C), ΔVd1 ‡/cm3 mol-1 = 2.0 ± 0.2, ΔVd2 ‡/cm3 mol-1 = -8.8 ± 1.0, ΔHd1 ‡/kJ mol-1 = 73.0 ± 0.9, ΔHd2 ‡/kJ mol-1 = 30 ± 5, ΔSd1 ‡/J mol-1 K-1 = -9 ± 3, and ΔSd2 ‡/J mol-1 K-1 = -140 ± 20; in MeCN, kd2/mol-1 kg s-1 = 73.5 ± 0.5, ΔVd2 ‡/cm3 mol-1 = -16.0 ± 0.8, ΔHd2 ‡/kJ mol-1 = 41.1 ± 1.3, and ΔSd2 ‡/J mol-1 K-1 = -71 ± 4. The reaction volume for the formation of NaCry+ in Me2SO has also been measured dilatometrically: ΔV° = 3.3 ± 0.4 cm3 mol-1. The reaction mechanism is discussed on the basis of these parameters.",
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AU - Ishihara, Koji

AU - Miura, Hiroko

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AU - Tanaka, Motoharu

PY - 1988

Y1 - 1988

N2 - The rate of dissociation of sodium cryptate(2,2,1) (NaCry+) has been measured at various temperatures and pressures in dimethyl sulfoxide (Me2SO), N,N-dimethylformamide (DMF), and acetonitrile (MeCN) by using a high-pressure stopped-flow apparatus with conductometric detection. There are two reaction paths: an acid-independent path (kd1), CryNa+ → Cry + Na+, and an acid-dependent path (kd2), CryNa+ + Hdca → CryH+ + Na+ + dca-, where Hdca is dichloroacetic acid. Activation parameters are as follows: in Me2SO, kd1/s-1 = (7.65 ± 0.05) × 10-1 (25°C), ΔVd1 ‡/cm3 mol-1 = 2.1 ± 0.7, ΔHd1 ‡/kJ mol-1 = 70.4 ± 0.8, and ΔSd1 ‡/J mol-1 K-1 = -11 ± 3; in DMF, kd1/s-1 = (3.37 ± 0.03) × 10-1 (25°C), kd2/mol-1 kg s-1 (25°C), ΔVd1 ‡/cm3 mol-1 = 2.0 ± 0.2, ΔVd2 ‡/cm3 mol-1 = -8.8 ± 1.0, ΔHd1 ‡/kJ mol-1 = 73.0 ± 0.9, ΔHd2 ‡/kJ mol-1 = 30 ± 5, ΔSd1 ‡/J mol-1 K-1 = -9 ± 3, and ΔSd2 ‡/J mol-1 K-1 = -140 ± 20; in MeCN, kd2/mol-1 kg s-1 = 73.5 ± 0.5, ΔVd2 ‡/cm3 mol-1 = -16.0 ± 0.8, ΔHd2 ‡/kJ mol-1 = 41.1 ± 1.3, and ΔSd2 ‡/J mol-1 K-1 = -71 ± 4. The reaction volume for the formation of NaCry+ in Me2SO has also been measured dilatometrically: ΔV° = 3.3 ± 0.4 cm3 mol-1. The reaction mechanism is discussed on the basis of these parameters.

AB - The rate of dissociation of sodium cryptate(2,2,1) (NaCry+) has been measured at various temperatures and pressures in dimethyl sulfoxide (Me2SO), N,N-dimethylformamide (DMF), and acetonitrile (MeCN) by using a high-pressure stopped-flow apparatus with conductometric detection. There are two reaction paths: an acid-independent path (kd1), CryNa+ → Cry + Na+, and an acid-dependent path (kd2), CryNa+ + Hdca → CryH+ + Na+ + dca-, where Hdca is dichloroacetic acid. Activation parameters are as follows: in Me2SO, kd1/s-1 = (7.65 ± 0.05) × 10-1 (25°C), ΔVd1 ‡/cm3 mol-1 = 2.1 ± 0.7, ΔHd1 ‡/kJ mol-1 = 70.4 ± 0.8, and ΔSd1 ‡/J mol-1 K-1 = -11 ± 3; in DMF, kd1/s-1 = (3.37 ± 0.03) × 10-1 (25°C), kd2/mol-1 kg s-1 (25°C), ΔVd1 ‡/cm3 mol-1 = 2.0 ± 0.2, ΔVd2 ‡/cm3 mol-1 = -8.8 ± 1.0, ΔHd1 ‡/kJ mol-1 = 73.0 ± 0.9, ΔHd2 ‡/kJ mol-1 = 30 ± 5, ΔSd1 ‡/J mol-1 K-1 = -9 ± 3, and ΔSd2 ‡/J mol-1 K-1 = -140 ± 20; in MeCN, kd2/mol-1 kg s-1 = 73.5 ± 0.5, ΔVd2 ‡/cm3 mol-1 = -16.0 ± 0.8, ΔHd2 ‡/kJ mol-1 = 41.1 ± 1.3, and ΔSd2 ‡/J mol-1 K-1 = -71 ± 4. The reaction volume for the formation of NaCry+ in Me2SO has also been measured dilatometrically: ΔV° = 3.3 ± 0.4 cm3 mol-1. The reaction mechanism is discussed on the basis of these parameters.

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