Попробуйте:
vendor_id = [1,2,3,4,5,6,7,8,9]
frequency = [5000,4000,3000,3500,880,500,400,300,300]
df = pd.DataFrame({'vendor_id':vendor_id, 'frequency':frequency})
df = df.sort_values('frequency', ascending=False)
fifth_frequency = df.iloc[4]['frequency']
df['vendor_id'] = df.apply(lambda x: x[0] if x[1]>=fifth_frequency else 9999, axis=1)