Synthesis and characterization of Hg(II) and Cd(II) complexes derived from the novel acenaphthaquinone-4-phenyl thiosemicarbazone and its CPE application

Figures & data

Table 1 Analytical and physical data of APTH and its complexes.

Compound	m.p. (°C)	Color	Elemental analyses; found (Calcd.)			Λm^a
			C	H	M
APTH	190	Brown	68.13 (68.86)	3.79 (3.95)	–	–
[Cd2(APTH)Cl4]	175	Red break	33.35 (32.69)	2.13 (1.88)	32.89 (32.21)	5.47
[Hg2(APTH)2Cl4(EtOH)2]	215	Reddish brown	39.11 (38.87)	2.51 (2.95)	31.18 (30.91)	18.50

a Ohm⁻¹.cm².mol⁻¹.

Fig. 1 IR spectrum of APTH in comparison to acenaphthoquinone.

Fig. 2 IR deconvolution analysis of APTH in the range 1710–1620 cm^−1.

Table 2 Infrared spectral date of APTH and its metal complexes in KBr.

Assignment	APTH	[Cd2(APTH)Cl4]	[Hg2(APTH)2Cl4(EtOH)2]
ν(N^4H)	3292	3290	3351
ν(N^2H)	3263	3236	3293
ν(C = O)free	1690^a	–	1702
ν(C = O)H-bonded	1680^a	1675^a	1683
ν(C = N^1)	1660^a	1655^a	1620
ν(C = C)	1600	1600	1600
Thioamide I	1540	1535	1577
Thioamide II	1430	1442	1456
Thioamide III	1168	1172	1174
ν(C = S)	828	802	827
ν(N–N)	1143	1145	1139
ν(C–O)	1049	1025	1031
ρ(NH)	750	732	730, 750

a Band obtained from deconvolution analysis.

Table 3 Deconvolution analysis parameters of the APTH IR spectrum in the range 1710–1620 cm⁻¹ (R² = 0.9986).

Peak type / No.	Center	Amplitude	FWHM	% Area
Gauss Amp 1	1660	4.94	39.41	32.81
Gauss Amp 2	1680	12.69	19.47	42.17
Gauss Amp 3	1690	9.97	14.71	25.02

Fig. 3 ¹H-NMR spectrum of APTH.

Structure 1 Structure of APTH.

Scheme 1 Fragmentation pattern of APTH.

Fig. 4 Electronic spectrum of APTH.

Fig. 5 IR deconvolution analysis of [Cd₂(APTH)Cl₄] in the range 1700–1620 cm^−1.

Structure 2 Structure of Cd(II) complex.

Table 4 Deconvolution analysis parameters of the [Cd₂(APTH)Cl₄] IR spectrum in the range 1700–1620 cm⁻¹ (R² = 0.9966).

Peak type / No.	Center	Amplitude	FWHM	% Area
Gauss Amp 1	1655	14.37	32.42	38.08
Gauss Amp 2	1675	34.08	22.23	61.92

Fig. 6 IR spectrum of [Hg₂(APTH)₂Cl₄(EtOH)₂].

Structure 3 Structure of Hg(II) complex.

Fig. 7 ¹H-NMR spectrum [Cd₂(APTH)Cl₄] complex.

Fig. 8 Effect of pH on the extraction recovery of Cd(II) and Hg(II) using APTH (10⁻⁵ M) and Triton X-114 (0.1 % w/v).

Fig. 9 Effect of APTH concentration on the extraction recovery of Cd(II) and Hg(II) using Triton X-114 (0.1 % w/v) at pH 7.

Fig. 10 Effect of Triton X-114 concentration on the extraction recovery % of the Cd(II) and Hg(II) using APTH (2 × 10⁻⁵ M) at pH 7.

Fig. 11 Effect of temperature on the extraction recovery % of the Cd(II) and Hg(II) using APTH (2 × 10⁻⁵ M) and Triton X-114 (0.1 %w/v) at pH 7.

Fig. 12 Effect of incubation time on the extraction recovery % of the Cd(II) and Hg(II) using APTH (2 × 10⁻⁵ M) and Triton X-114 (0.1 %w/v) at pH 7.

Fig. 13 Calibration curve of the Cd(II) using APTH (2 × 10⁻⁵ M) and Triton X-114 (0.1 %w/v) at pH 7.

Fig. 14 Calibration curve of the Hg(II) using APTH (2 × 10⁻⁵ M) and Triton X-114 (0.1 % w/v) at pH 7.

Table 5 Tolerance limits for interference ions.

Interfering ion	Cd(II)		Hg(II)
	Tolerance limit	Recovery %	Tolerance limit	Recovery %
K^+	1000	105.23	1000	99.46
Na^+	1000	101.87	1000	98.34
Mg^2+	1000	98.58	1000	100.34
Ca^2+	1000	99.92	1000	99.88
Fe^2+	1	98.63	1	99.69
Fe^3+	1	100.01	1	102.42
Al^3+	10	109.23	2	99.94
F^−	25	98.95	10	97.07
Cl^−	1000	98.23	1000	97.34
I^−	300	97.28	100	98.47
NO3^−	1000	102.77	1000	99.93
SO4^2−	100	103.22	100	99.69
PO4^3−	80	99.67	30	98.22
SCN^−	150	99.50	50	97.64
Thiourea	200	96.50	100	97.79
Oxalate	20	98.18	1	98.55
Citrate	5	99.71	2	102.45

Table 6 Determination of the Hg(II) and Cd(II) in 50 ml water samples using the presented CPE procedure in comparison with those obtained by FAAS.

Water sample (location)	Cd(II) (ng/ml)		Hg(II) (ng/ml)
	Spectrophotometrically	FAAS	Spectrophotometrically	CVAAS
Tape (Mansoura)	0.15	0.145	0.12	0.11
River Nile (Mansoura)	0.03	0.03	0.05	0.04
El-Manzala lake (El-Manzala)	0.17	0.18	0.70	0.65
Mediterranean Sea (Gamasa)	0.22	0.21	0.34	0.35
Underground (Belqas territory)	0.13	0.14	0.17	0.16

Table 7 CPE applications for metal ions analysis of the current work in comparison with previous studies.

Ion	Reagent	Surfactant	Detection system	DL (mg/l)	Matrix	References
Hg(II)	5-Br-PADAP	PONPE7.5	ETAAS	0.01	Human hair; urine and water	[54]
	APDC	TritonX-114	ICP-Ms	0.005	River, bottled, reservoir and tap water	[55]
	Dithiazone	TritonX-100	Spectrophotometry	0.014	Natural water	[56]
	PAN	TritonX-114	Spectrophotometry	1.65	River, lake and tap water	[57]
	APTH	TritonX-114	Spectrophotometry	2.0	River, lake, underground and tap water	Current work
Cd(II)	5-Br-PADAP	PONPE7.5	ETAAS	0.008	Urine, water	[58]
	APDC	TritonX-114	ICP-Ms	0.002	River, bottled, reservoir and tap water	[55]
	Dithiazone	TritonX-114	ICP-OES	0.093	Petroleum produced water	[57]
	PAN	TritonX-114	ICP-OES	4.0	Dolomite and bone ash	[58]
	APTH	TritonX-114	Spectrophotometry	1.0	River, lake, underground and tap water	Current work