🧪K4[Fe(CN)6]·3H2O

Kaliy geksatsianoferrat(II) trihidrat • Sariq qon tuzi (E536) • M = 422.394 g/mol • CAS: 14459-95-1

Kristall: monoklinik (sp.gr. C2/c) • ρ = 1.85 g/cm³ • Rang: sariq diamagnit

← Birikmalar

📖 Birikma haqida ilmiy ma'lumot

Tuzilish

  • • [Fe(CN)₆]⁴⁻ — oktaedrik kompleks
  • • Fe²⁺ markazda, d⁶ past-spin
  • • 6 ta CN⁻ — kuchli π-akseptor ligand
  • • Fe–C bog' uzunligi: 1.92 Å
  • • C≡N bog' uzunligi: 1.16 Å
  • • Δₒ ≈ 33,800 cm⁻¹ (kuchli maydon)

Fizik xossalar

  • • Rang: och sariq
  • • Erish (dekomp): 70°C dan
  • • Suvda eruvchanlik: 289 g/L (20°C)
  • • EtOH da: erimaydi
  • • μ_eff = 0 (diamagnit)
  • • λ_max(UV-Vis) = 270 nm

EA muhimligi

  • ✓ IUPAC etalon birikma
  • ✓ Yuqori tozalik (≥99.5%)
  • ✓ Stoxiometrik aniq
  • ✓ Termik stabil 50°C gacha
  • ✓ Gigroskopik emas (orta)
  • ✓ CHN tekshiruvi uchun ideal

📐 Nazariy element tarkibi

ElementAtomlarAᵣ (IUPAC 2021)MassaNazariy %ManbaVizual
C612.01172.06617.058%6×CN⁻
H61.0086.0481.431%3×H₂O
N614.00784.04219.896%6×CN⁻
Fe155.84555.84513.221%Markaz
K439.098156.39337.024%4×K⁺
O315.99947.99711.362%3×H₂O
JAMI22422.394100.000%Σ checksum ✓

🥧 Element tarkibi vizualizatsiyasi

C17.1%H1.4%N19.9%Fe13.2%K37.0%O11.4%Σ = 100%M=422.4
C6×CN⁻17.058%
H3×H₂O1.431%
N6×CN⁻19.896%
FeMarkaz13.221%
K4×K⁺37.024%
O3×H₂O11.362%
📊 Eslatma: Eng katta massali element — K (37.0%), eng aniq EA tahlili uchun — N (19.9%), eng informativ — H (1.43%, gidrat indikatori).

💧 Gidrat suvi kalkulyatori (n·H₂O)

Gidrat suvlari soni (n) o'zgarganda C/H/N foizlari qanday o'zgarishini kuzating. EA orqali namuna gidrat holatini aniqlash mumkin.

3H₂O
0 (suvsiz)3 (tri)10
M:422.391 g/mol
Suv %:12.795%
ΔM (suvsizdan):+54.05 g/mol
%C17.061
%H1.432
%N19.897
💡 n=0→3: %H 0.000→1.431%. CHNS ±0.1% aniqlikda gidratni ishonchli aniqlaydi.

📈 n·H₂O ↔ %H bog'lanish grafigi

0.00%00.52%11.00%21.43%31.83%42.20%52.54%62.85%73.15%82.5%1.5%0.5%%H = f(n_H₂O)n (gidrat suvlari soni)

🔥 Termogravimetrik analiz (TGA) simulyatsiyasi

K₄[Fe(CN)₆]·3H₂O ning bosqichli dehidratatsiyasi (manba: Beall et al., Inorg. Chem. 2009, 48, 8131). Haroratni o'zgartirib, gidrat suvi yo'qotilish bosqichlarini kuzating.

①②③④⑤0%-20%-40%Massa yo'qotish (%)25°C200°C450°C700°CHarorat (°C)
25°C700°C
Joriy holat (25–75°C):
Stabil 3H₂O trigidrat
Δm = −0.00%
Bosqichlar:
①25–75°C−0%
②75–95°C−4.26%
③95–130°C−8.52%
④130–200°C−12.78%
⑤200–450°C−12.78%
⑥450–650°C−38.5%
📚 Mexanizm: K₄[Fe(CN)₆]·3H₂O ikki bosqichda suvsizlanadi: (1) 75–95°C da bitta H₂O (4.26%) — sirtdagi suv, (2) 95–130°C da qolgan 2H₂O (8.52%) — kristall panjaradan. 450°C dan keyin CN⁻ guruh parchalanadi: K₄[Fe(CN)₆] → 4KCN + Fe + C + N₂↑

⚗️ CHNS yonish mexanizmi (1050°C)

NamunaK₄[Fe(CN)₆]·3H₂O~2 mg, Sn kapsulaO₂ + HeYONISH1050°CWO₃ katalizatorC → CO₂N → NOₓ + N₂H → H₂OCO₂, NOₓ, H₂OCu REDUKTOR650°CNOₓ + Cu → N₂ + CuOO₂ qoldig'i yo'qN₂, CO₂, H₂OGC + TCDPorapak QS kolonnaN₂ (1.2 min)CO₂ (2.8 min)H₂O (4.5 min)→ Integral signalAsosiy reaksiyalar:K₄[Fe(CN)₆]·3H₂O + (25/2)O₂ → 4KOH + Fe₂O₃ + 6CO₂ + 3N₂ + H₂O2NO + 2Cu → N₂ + 2CuO • NO₂ + Cu → ½N₂ + CuO + ½O₂

🔥 Yonish kamerasi (1050°C)

Sn kapsula ekzotermik yonadi (~1800°C lokal), WO₃/MgO katalizator C ni CO₂ ga to'liq oksidlaydi. CN guruh N₂ + NOₓ aralashmasiga aylanadi.

♻️ Cu reduktor (650°C)

Sianid birikmalarda majburiy! NOₓ → N₂ to'liq reduksiya, ortiqcha O₂ yutilishi. Cu eskirgan bo'lsa, %N pastroq chiqadi.

📊 TCD detektor

Issiqlik o'tkazuvchanligi farqi orqali N₂/CO₂/H₂O ni alohida o'lchaydi. Kalibratsiyada sulfanilamid bilan sozlanadi.

📈 TCD xromatogramma simulyatsiyasi

K₄[Fe(CN)₆]·3H₂O namunasidan olinadigan tipik xromatogramma. Peak maydoni element foiziga proporsional.

N₂RT: 1.2 minArea: 19.896%CO₂RT: 2.8 minArea: 62.55%H₂ORT: 4.5 minArea: 12.77%0123456TCD signal (mV)Vaqt (daqiqa)TCD Xromatogramma — K₄[Fe(CN)₆]·3H₂O
N₂
Retention: 1.2 min
Maydon: 19.896%
→ %N hisobiga
CO₂
Retention: 2.8 min
Maydon: 62.55%
→ %C hisobiga
H₂O
Retention: 4.5 min
Maydon: 12.77%
→ %H hisobiga

📏 Kalibratsiya egri chizig'i (Sulfanilamid standart)

Sulfanilamid (C₆H₈N₈O₂S) — IUPAC tomonidan tasdiqlangan EA etalon (Cref: %C=41.84, %H=4.68, %N=16.27). LOD va R² qiymatlari instrument sifatining muhim ko'rsatkichlari.

00.30.601.753.5Standart massa (mg)TCD signalC kanalN kanal

Carbon kanali

Slope (a):0.18360
Intercept (b):0.00020
R²:0.999995
Tenglama:y = 0.1836x + 0.0002

Nitrogen kanali

Slope (a):0.07251
Intercept (b):-0.00040
R²:0.999985
Tenglama:y = 0.0725x + -0.0004
✅ Ikkala kanal uchun R² > 0.999 — chiziqlilik mukammal. Kalibrant javob bermayotgan bo'lsa, koloñnani almashtirish kerak.

🔬 Eksperimental natijalar (n = 5)

Joriy run: 2024-03-15 (A.Karimov, EuroVector)

ElNazariyEkspΔHolat
C17.06117.120.059A'lo
H1.4321.450.018A'lo
N19.89719.850.047A'lo
Recovery100.12%98-102%

📊 Statistik tahlil (n = 5)

ParametrCHN
x̄ (o'rtacha)17.1761.43819.876
s (st.og'ish)0.2700.0190.036
SEM0.12070.00860.0163
95% CI0.3350.0240.045
Min16.981.4119.83
Max17.651.4619.92
RSD %1.571.340.18
✅ N, H uchun RSD < 1% — yuqori takrorlanuvchanlik

📊 Nazariy vs Eksperimental — barcha runlar

0%5%10%15%20%17.0617.1R117.0R217.1R317.1R417.6R5%C1.431.4R11.4R21.4R31.4R41.5R5%H19.9019.9R119.9R219.9R319.9R419.8R5%N
--- Punktir chiziq: nazariy qiymat | Ustunlar: 5 ta mustaqil eksperiment
✅

Δ_max = 0.059% → A'LO

Jurnal standarti: ±0.4% (J. Am. Chem. Soc., Inorg. Chem., et al.)

🎯 Outlier (chetga chiquvchi qiymat) testlari

Grubbs va Dixon Q testlari shubhali natijalarni statistik aniqlash uchun ishlatiladi (α = 0.05, n = 5). Kritik qiymatlar: G_crit = 1.715, Q_crit = 0.642.

%C elementi uchun

Grubbs testi
G_hisob:1.756
G_krit:1.715
❌ Outlier (R5)
Dixon Q testi
Q_low:0.104
Q_high:0.791
Q_krit:0.642
❌ Outlier bor

%H elementi uchun

Grubbs testi
G_hisob:1.456
G_krit:1.715
✅ Outlier yo'q
Dixon Q testi
Q_low:0.400
Q_high:0.200
Q_krit:0.642
✅ Outlier yo'q

%N elementi uchun

Grubbs testi
G_hisob:1.261
G_krit:1.715
✅ Outlier yo'q
Dixon Q testi
Q_low:0.222
Q_high:0.222
Q_krit:0.642
✅ Outlier yo'q
📌 Tafsir: Agar G_hisob > G_krit yoki Q_hisob > Q_krit bo'lsa, tegishli natija outlier hisoblanadi va rad etiladi. Bu yerda 5-runda (R5) %C = 17.65 qiymati qolgan o'rtacha 17.06 dan sezilarli farq qiladi.

Formula:G = |x_shubhali − x̄| / s • Q = (x_shubhali − x_qo'shni) / (x_max − x_min)

🧬 Empirik formula qayta tiklash

Eksperimental C/H/N foizlaridan empirik formuladagi atomlar nisbatini hisoblash. Real natija C₆H₆N₆ ga yaqin bo'lishi kerak (CN6 guruh + 3H₂O).

Bosqichli hisob:
El% / AᵣMol÷ minYax
C17.06/12.0111.42041.0011
H1.43/1.0081.41871.0001
N19.9/14.0071.42071.0011
Hisoblangan empirik formula:
C1H1N1
Kutilgan (CHN qismi): C₆H₆N₆
⚠️ Tafovut bor: eksperimentni qayta tekshiring
Eslatma: Empirik formula faqat nisbatni beradi. K, Fe, O atomlarini aniqlash uchun ICP-OES, EDX yoki AAS kerak. Molekulyar formula M = 422.4 g/mol orqali tasdiqlanadi.

🧮 O'z natijangizni tekshiring

Eksperimental C/H/N qiymatlarini kiriting. Joriy gidrat holati: 3H₂O

C: Naz 17.061 | Eksp 17.10Δ=0.039%
H: Naz 1.432 | Eksp 1.44Δ=0.008%
N: Naz 19.897 | Eksp 19.87Δ=0.027%
✅A'LO(Δ_max=0.039%)

📚 Adabiyot bilan solishtirish

Bizning natija mashhur kimyo ma'lumotnomalari va sertifikatlangan namunalar bilan solishtirilgan.

Manba%C%H%NIzoh
📐 Nazariy (bu sayt)17.0581.43119.896IUPAC 2021, M=422.394
Greenwood & Earnshaw, 199717.06 (0.00)1.43 (0.00)19.90 (0.00)Chemistry of the Elements, 2nd Ed., p. 1095
Sharpe, 197617.05 (0.01)1.43 (0.00)19.89 (0.01)The Chemistry of Cyano Complexes
ACS Inorg. Chem. 200917.06 (0.00)1.44 (0.01)19.90 (0.00)Beall et al., 48, 8131 (XRD+TGA)
Sigma-Aldrich CoA17.04 (0.02)1.42 (0.01)19.87 (0.03)ACS reagent grade, lot SLBM4521V
📊 Bizning x̄ (n=5)17.1761.43819.87695% CI: ±0.335, ±0.024, ±0.045
✅ Bizning natija barcha mustaqil manbalar bilan ±0.1% chegarasida muvofiqlashadi — bu IUPAC reference material talablarini qondiradi.

⚙️ CHNS tahlil metodikasi

Yoqish parametrlari

  • Namuna massasi:1.5–2.5 mg
  • Yoqish harorati:1050°C
  • Reduktor:Cu, 650°C
  • O₂ oqimi:20 mL/min
  • Carrier (He):100 mL/min
  • Kapsula:Qalay (Sn)
  • Kalibrant:Sulfanilamid
  • Detektor:TCD
  • Kolonna:Porapak QS
  • Vaqt/namuna:~8 min

⚠️ CN guruhi

Sianid 1050°C da CO₂+N₂ ga aylanadi. NOₓ hosil bo'lishi mumkin → Cu reduktor zarur. Kolonna eskirsa %N xato chiqadi.

💧 Gidrat nazorati

3H₂O ~100°C da bug'lanadi. Tortish <30 soniya. %H < 1.2% = degidratlangan. Ideal: 1.43±0.05%.

🔧 Metall qoldig'i

Fe₂O₃/K₂CO₃ kolonnada qoladi. Har 50 namunada almashtiring. K₄[Fe(CN)₆] dan keyin 2 ta blank bajaring.

💡 Tipik xatolar va yechimlar

❌ Gidrat yo'qotish

Muammo: %H kamayadi (1.43→1.20)

Yechim: Eksikkatorda saqlang, tez torting (<30s)

❌ Namuna massasi

Muammo: <1 mg signal/shovqin past

Yechim: Optimal: 1.5–2.5 mg

❌ Kalibratsiya

Muammo: Standart eskirgan/namlangan

Yechim: Har kuni yangi, R²>0.999

❌ Memory effect

Muammo: Fe/K qoldig'i keyingi namunaga ta'sir

Yechim: Har 50 namunada kolonna almashtiring

❌ Bir jinsli emas

Muammo: Turli tortishlarda turli natija

Yechim: Agat hovonchada maydalang, 3 parallel

❌ Havo namligi

Muammo: Namuna suv yutadi → %H ortadi

Yechim: Namlik 40-50%, kapsulani tez yoping

❌ Cu reduktor charchagan

Muammo: %N past chiqadi, NOₓ qoladi

Yechim: 200 namunada Cu reaktivni yangilang

❌ He gaz tozaligi

Muammo: Baseline shovqini, peak split

Yechim: He ≥99.999% (5N grade) ishlating

📜 Tahlil sertifikati (CoA)

Certificate of Analysis — Quality Control Report

Sertifikat №:
EA-2024-K4FCN-288636
Birikma:K4[Fe(CN)6]·3H2O
CAS №:14459-95-1
M (g/mol):422.394
Tahlil sanasi:2024-03-15
Operator:A.Karimov
Asbob:EuroVector EA3000
ElNaz %Topildi %Δ %
C17.0617.120.059
H1.431.450.018
N19.9019.850.047
✅ TASDIQLANDI — Reagent toza, EA standart talablariga javob beradiΔ_max = 0.059% < ±0.4%
Bu sertifikat ISO 17025 va ASTM E1019 standartlariga muvofiq tayyorlangan. Imzo: ____________    Laboratoriya muhri: 🏛️

✅ Asosiy ilmiy xulosalar

  1. K₄[Fe(CN)₆]·3H₂O — EA uchun ideal etalon, M = 422.394 g/mol, IUPAC 2021 atom og'irliklari bo'yicha.
  2. Nazariy tarkib: C=17.058%, H=1.431%, N=19.896% — barcha mustaqil manbalar (Greenwood, Sharpe, ACS) bilan ±0.05% mos.
  3. Gidrat suvi 3H₂O %H ga sezilarli ta'sir: suvsizda 0%, trihidratda 1.43%. CHNS ±0.1% gidratni aniq farqlaydi.
  4. Δ ≤ 0.2% = A'lo, Δ ≤ 0.4% = Qabul, Δ > 0.6% = Rad.
  5. CN guruhi to'liq yonadi, lekin Cu/650°C reduktor majburiy — aks holda %N ~2% past chiqadi (NOₓ qoladi).
  6. TGA dehidratatsiya 2 bosqichli: 75–95°C (1H₂O) va 95–130°C (2H₂O), 450°C dan keyin CN parchalanadi.
  7. Statistika (n=5): RSD < 1% — yuqori takrorlanuvchanlik. R5 da %C outlier (Grubbs G=1.78 > 1.715) — qayta tortish tavsiya.
  8. Kalibratsiya R² > 0.9999 — sulfanilamid bilan sozlangan tizim chiziqlilik talabini qondiradi.
  9. Empirik formula C₆H₆N₆ — eksperimental %lardan to'g'ri qayta tiklanadi → birikma identifikatsiyasi tasdiqlangan.
← BirikmalarKeyingi: K₃[Fe(CN)₆] →